Thesis presented for obtaining the degree of
DOKTOR DER NATURWISSENSCHAFTEN
(Doctor rer. nat.)
Tripod-shaped Organotin Compounds: Complexation Studies
towards Lewis Bases and Chalcogenido Clusters of Unprecedented
Nuclearity
Dipl.-Ing. Jihed Ayari
First Reviewer: Prof. Dr. Klaus Jurkschat
Second Reviewer: Privatdozent Dr. Uwe Zachwieja
ACKNOWLEDGMENT
The present work was carried out from July 2014 until September 2018 at the Institute of
Inorganic Chemistry of the Technische Universität Dortmund
under the supervision of
P R O F . D R . K L A U S J U R K S C H AT
whom I pay my greatest gratitude and thanks for the interesting topic, for his skilful guid-
ance and encouragement throughout the course of this research, for his human relationship
and moral support. You are always my source of admiration.
My sincere thanks and regards go also to
P R I VAT D O Z E N T D R . U W E Z A C H W I E J A
for writing the second review report.
My sincere thanks are also extended to all the scientific co-workers of the research group of
Prof. Dr. K. JURKSCHAT for their moral and technical support during my entire journey
of research.
In particular, I would like to thank:
Dr. H A Z E M E L N A S R, Dr. M I C H A E L L U T T E R, and Dr. C H R I S T I A N R . G Ö B
for performing the X-ray diffraction analyses.
Prof. Dr. W O L F H I L L E R
for NMR spectroscopic measurements and help concerning the interpretation of data.
Mrs. S Y LV I A M A R Z I A N and Ms. L A U R A S C H N E I D E R
for ESI Mass spectrometry measurements.
I also appreciate the technical staff for their day-to-day services.
I express my heartful gratitude for my husband Yassine for his presence, his emotional
and moral support that helped me to continue the path under all circumstances. He always
stood by my side and still, for that a big THANK YOU!
My profound thanks goes to my Mom Habiba and Dad Mokhtar who believed in me
unconditionally and still along my life. They are the source of my continuous optimism,
even in the darkest moments. I affectional thank my beloved sister Nidhal and my brother
Mohamed, for their encouragement, love and care all along my life, my cheerful niece
Fatima Zahraa for her sweet smiley face, that spread happiness and hope, wherever she
goes.
My Dearest “Tata Mounira” peace upon her soul, to whom I dedicate this work. I deeply
thank my father-in-law Jalel for his support and encouragements. My sweet thoughts go
to my dear grandfathers, my dearest grandmother Halima, peace upon their souls, and to
my beloved grandmother Baya.
Finally, I would like to thank all my family’s members and friends who encourage me,
even with a smile, throughout this journey.
“Die Gelehrten sind die Erben der
Propheten. Die Propheten haben keinen
Dinar oder Dirham geerbt, sondern sie
haben das Wissen geerbt, und wer immer es
nimmt, hat reichlich Glück erhalten”, sagte
der Prophet Mohammed, Gott segne ihn
und schenke ihm Frieden.
Dinar, Dirham: alte Goldwährung in der arabis-
chen Welt.
CONTENTS
Contents
Contents 1
List of Figures 4
Table of Schemes 9
List of Charts 11
List of Tables 12
List of Abbreviations 13
1 General Introduction 14
1.1 Host-Guest Approach in Supramolecular Chemistry . . . . . . . . . . . . 14
1.2 Organotin Compounds in Host-Guest Chemistry . . . . . . . . . . . . . . 15
2 Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph,
CH2SiMe3), its Characterization, and its Complexation Behaviour toward
Lewis-Bases 20
2.1 Syntheses and characterization of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X =
I, F, Cl, Br; R = Ph, CH2SiMe3) . . . . . . . . . . . . . . . . . . . . . . 20
2.2 Reactivity of halogen-substituted derivatives MeSi(CH2SnR(3 – n)Xn)3 (n
= 1– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3) towards anions and neutral
Lewis-Bases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
2.2.1 Complexation behaviour of 4 and 12 towards chloride anions and
HMPA, respectively . . . . . . . . . . . . . . . . . . . . . . . . 39
2.2.2 Complexation behaviour of 6 towards HMPA molecules and chlo-
ride anions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
2.2.3 Complexation behaviour of 7 towards fluoride anions . . . . . . . 61
2.2.4 Complexation behaviour of 5 towards acetate anions . . . . . . . 67
2.2.5 Complexation behaviour of 9 towards bromide anions . . . . . . 72
2.3 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
2.4 Experimental Section . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
3 The Spacer-Bridged Tetrastannanes R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X =
I, Cl; R = Ph, R'= R, X), Syntheses, Structures and Complexation Studies 94
1
CONTENTS
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
3.2 Syntheses and characterization of R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X =
I, Cl; R = Ph, R'= R, X) . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
3.3 Attempts for the complexation of chloride anions via ClSn(CH2SnPhCl2)3, 3103
3.4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
3.5 Experimental section . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
4 MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as
Precursors for Unprecedented Diorganotin Oxo Clusters and Adamantane-
like Structures 114
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
4.2 New ladder-type containing diorganotin oxo-clusters . . . . . . . . . . . 116
4.3 Novel S-, Se- containing silastannaadamantanes: syntheses, structures, and
redistribution reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
4.4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
4.5 Experimental section . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
5 The Unprecedented Octanuclear Organotin Oxo Cluster
{[MeSi(MeSnCl)(CH2)3(µ3 – O)(MeSnCl)(CH2)3]2O}2 187
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
5.2 Synthesis and structure . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
5.3 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
5.4 Experimental section . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
6 Novel Triorganotin-functionalized Aminoalcohol Derivatives as Potential Pre-
cursors for the Synthesis of Organtin-containing Azidocryptands 192
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
6.2 Synthesis of Ph3Sn(CH2)2N[CH2C(CH3)2OH]2 and its reaction with tetra-
tert-butoxystannane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
6.3 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
6.4 Experimental section . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
7 Summary 203
8 Zusammenfassung 211
9 References 219
List of New Compounds 223
Affidavit 242
2
LIST OF FIGURES
List of Figures
1 Examples of the most known characteristic host-guest complexes. . . . . 15
2 Examples of multidentate organostannate complexes. . . . . . . . . . . . 16
3 Examples for tetraorganodistannoxanes showing double- and triple-ladder
structures, respectively. . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4 General view (POV-Ray) of a molecule of 2. . . . . . . . . . . . . . . . . 21
5 119Sn NMR spectrum (149.26 MHz, CDCl3) of compound 2. . . . . . . . 22
6 119Sn NMR spectrum (149.26 MHz, CDCl3) of compound 3. . . . . . . . 24
7 119Sn NMR spectrum (149.26 MHz, C6D6) of compound 4. . . . . . . . . 26
8 119Sn NMR spectra of compound 5 (149.26 MHz, CDCl3) (left) and 6
(223.85 MHz, CDCl3) (right). . . . . . . . . . . . . . . . . . . . . . . . 30
9 General view (POV-Ray) of a molecule of 6 . . . . . . . . . . . . . . . . 31
10 General view (POV-Ray) of a molecule of 9. . . . . . . . . . . . . . . . . 33
11 Polymeric chain of 9 established through Br· · ·Sn and Br· · ·Br intermolec-
ular interactions (shown with broken lines). . . . . . . . . . . . . . . . . 33
12 119Sn NMR spectra of compound 8 (223.85 MHz, C6D6) (left) and 9
(149.26 MHz, CDCl3) (right). . . . . . . . . . . . . . . . . . . . . . . . 35
13 1H NMR spectrum (600.29 MHz, CDCl3) of compound 10. . . . . . . . . 37
14 119Sn NMR spectra (223.85 MHz, CDCl3) of 10, 11 (149.26 MHz, CDCl3)
and 12 (149.26 MHz, C6D6) (from left to right). . . . . . . . . . . . . . . 37
16 General view (POV-Ray) of a molecule of 14 showing crystallographic
numbering scheme. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
17 General view (POV-Ray) of a molecule of 25 showing crystallographic
numbering scheme. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
18 General view (POV-Ray) of a molecule of 16 showing crystallographic
numbering scheme for Sn(1). . . . . . . . . . . . . . . . . . . . . . . . . 50
19 A POV-Ray image in sticks of a molecule of 16 showing bowl-alike molec-
ular structure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
20 General view (POV-Ray) of a molecule of 18 showing the two molecules
in one-unit cell with the crystallographic numbering scheme. . . . . . . . 53
21 General view (POV-Ray) of a molecule of 19 showing the crystallographic
numbering scheme. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
22 119Sn NMR spectrum of a crystals sample at −80 ◦C (149.26 MHz, CDCl3)
of complexes 18 and 19. . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3
LIST OF FIGURES
23 31P NMR spectrum of a crystals sample at −80 ◦C (162.02 MHz, CD2Cl2)
of compound 18 + 19. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
24 General view (POV-Ray) of a molecule of 22 showing the crystallographic
numbering scheme. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
25 19F NMR spectrum (564.84 MHz, CD3CN) at ambient temperature of the
mixture containing 7 and two molar equiv of NEt4F ·2H2O. . . . . . . . . 64
26 The dianionic fluoridostannate 22, presenting the different terminal and
bridging tin and fluorine atoms. . . . . . . . . . . . . . . . . . . . . . . . 64
27 19F NMR spectrum (564.84 MHz, CD3CN) at ambient temperature of a
mixture containing 7 and three molar equiv of NET4F ·2H2O. . . . . . . 65
28 119Sn NMR spectrum (223.85 MHz, CD3CN) at ambient temperature of
compound 7 to which three molar equiv of NEt4F ·2H2O had been added. 66
29 General view (POV-Ray) of a molecule of 17 showing the crystallographic
numbering scheme. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
30 119Sn NMR spectrum of crystals sample of 17 at room temperature
(400.25 MHz, CDCl3). . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
31 The acetate triorganostannate 17, presenting the different tin atoms Sn1,
Sn1'and Sn2 atoms of the eight- and 16-membred rings in the skeleton. . . 69
32 IR spectrum of acetate complex 17, in which the C –– O absorption stretch
and the C – O stretching bands. . . . . . . . . . . . . . . . . . . . . . . . 69
33 POV Ray images of 17 in space fill mode (left with protons, right: without
protons). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
34 General view (POV-Ray) of a molecule of 23 ·0.5CH2Cl2 showing crys-
tallographic numbering scheme. . . . . . . . . . . . . . . . . . . . . . . 74
35 General view (POV-Ray) of a molecule of 24 showing crystallographic
numbering scheme. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
36 General view (POV-Ray) of a molecule of 2 showing the crystallographic
numbering scheme. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
37 119Sn NMR spectrum (149.26 MHz, CDCl3) of compound 2. . . . . . . . 97
38 119Sn NMR spectrum (111.92 MHz, CDCl3) of compound 3. . . . . . . . 98
39 General view (POV-Ray) of a molecule of 4 showing the crystallographic
numbering scheme. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
40 119Sn NMR spectrum (111.92 MHz, CDCl3) of compound 4. . . . . . . . 101
41 119Sn NMR spectrum of crude mixture of the reaction of formation of 6
and 7 at ambient temperature (149.26 MHz, CDCl3). . . . . . . . . . . . 104
42 General view (POV-Ray) of a molecule of 6 showing crystallographic
numbering scheme. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
4
LIST OF FIGURES
43 General view (POV-Ray) of a molecule of 7 showing the crystallographic
numbering scheme. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
44 General view (POV-Ray) of a molecule of 8 ·0.5H2O showing crystallo-
graphic numbering scheme. . . . . . . . . . . . . . . . . . . . . . . . . . 108
45 General view (POV-Ray) of a molecule of 9 showing crystallographic
numbering scheme and NH· · ·Cl intramolecular interactions with the pyri-
dinium cations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
46 POV-Ray image of the molecular structure of
[(MeSi(CH2)3)Sn(µ3-O)3(Ph)Sn(Cl)(Ph)Sn(µ2-OH)(Ph)Sn(t-Bu)]2,
26. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
47 Configuration of the trigonal bipyramidal endo-tin atoms Sn(1), Sn(2) and
Sn(3A) and the exo-cyclic tin atom Sn(4A) of compound 26. . . . . . . . 118
48 1H NMR spectrum (600.29 MHz, C6D6) of crystals sample of 26: hole
spectrum and aliphatic part are shown. . . . . . . . . . . . . . . . . . . . 121
49 119Sn NMR spectrum (223.85 MHz, CDCl3) of crystals sample of 26. . . 122
50 POV-Ray image of the molecular structure of
{[MeSi(CH2)3]SnCl(CH2SiMe3)(µ3-O)SnCl(CH2SiMe3)Sn(µ3-
O)(Cl)2(CH2SiMe3)Sn(t-Bu)2}, 27. . . . . . . . . . . . . . . . . . . . . 124
51 Different perspectives of the adamantine-like structure
[MeSi(CH2SnCH2SiMe3)3(O)Cl2] coordinated with µ3-O and a t-
Bu2SnCl2 molecule. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
52 POV-Ray image of the molecular structure of
{[MeSi(CH2)3]SnI(CH2SiMe3)(µ2-OH)[SnO(CH2SiMe3)]2Sn(µ2-OH)I
Sn(t-Bu)2}, 28. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
53 Different perspectives of the the adamantine-like structure
[MeSi(CH2SnOCH2SiMe3)3] coordinated with one H2O and a t-Bu2SnI2
molecules. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
54 119Sn NMR spectrum (149.26 MHz, CDCl3) of crystals sample of 28. . . 133
55 Top: General view (ball and stick) of a molecule of the organotin oxide 29
containing the numbering of the atoms that appear below in the listing of
distances and angles. Bottom: Side view of a molecule of 29 including the
numbering for the silicon atoms. . . . . . . . . . . . . . . . . . . . . . . 135
56 Front view a) and side view b) (POV-Ray) of 29. . . . . . . . . . . . . . 136
57 Simplified structure of 29 showing the non-equivalence of the SiCH3 moi-
eties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
58 Crystal packing of 29. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
59 Illustration of the C – H· · ·pi interactions at a H(144)-centroid (C171–
C176) centroid distance of 2.89(1) Å. . . . . . . . . . . . . . . . . . . . . 138
5
LIST OF FIGURES
60 1H NMR spectrum (500.08 MHz, CDCl3) of compound 29. . . . . . . . . 139
61 1H NMR spectrum (500.08 MHz, CDCl3) of compound 29 (aliphatic part). 140
62 2D 1H DOSY NMR spectrum of [MeSi(CH2SnPhO)3]6, 29, in CDCl3. . . 140
63 Top: General view (ball and stick) of a molecule of the organotin oxide 30
containing the numbering of the atoms that appear below in the listing of
distances and angles. Bottom: Side view of a molecule of 30 including the
numbering for the silicon atoms. . . . . . . . . . . . . . . . . . . . . . . 143
64 Simplified molecular structure of 30 illustrating the positions of the SiCH3
moieties and the substituents at the tin atoms pointing inside the cavity. . 144
65 Front view a) and side view b) (POV-Ray) of 30. . . . . . . . . . . . . . 144
66 Crystal structure of 30. . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
67 119Sn NMR spectrum of the crude mixture (149.26 MHz, CDCl3) giving
compound 29 and 31. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
68 POV-Ray image presented in balls and sticks of the molecular structure of
[(MeSi(CH2)3)Sn(µ3-O)3(Ph)Sn(I)(Ph)Sn(µ2-OH)(Ph)Sn(t-Bu)2]2, 31. . . 149
69 Presentation of 31 as one-third moiety of 29; [MeSi(CH2SnOPh)3]2 with
coordination with two t-Bu2SnIOH molecules. . . . . . . . . . . . . . . . 150
70 Different perspectives of the three ladder-like structures connected via
nine Sn2O2 rings in the skeleton of 32. . . . . . . . . . . . . . . . . . . . 152
71 POV-Ray image of the molecular structure of
[MeSi(CH2SnBr)3(µ2-OH)2(µ4-O)(µ3-OEt)2]2 ·2EtOH, 32. . . . . . . . . 153
72 119Sn NMR spectrum (223.85 MHz, CDCl3) of the crude mixture of the
reaction of formation of of 33. . . . . . . . . . . . . . . . . . . . . . . . 155
73 Left: POV-Ray image of the molecular structure of MeSi(CH2SnPhS)3.
Right: Overall symmetry of 33. . . . . . . . . . . . . . . . . . . . . . . . 156
74 119Sn NMR spectrum (149.26 MHz, CDCl3) of compound 33. . . . . . . 158
75 119Sn NMR spectrum (223.85 MHz, CDCl3) of the crude mixture of the
reaction of formation of 34. . . . . . . . . . . . . . . . . . . . . . . . . . 159
76 Left: POV-Ray image of the molecular structure of MeSi(CH2SnPhSe)3,
34. Right: Overall symmetry characteristic of 34. . . . . . . . . . . . . . 161
77 119Sn NMR spectrum (149.26 MHz, CDCl3) of compound 34. . . . . . . 163
78 77Se NMR spectrum (223.85 MHz, CDCl3) of compound 34. . . . . . . . 164
79 119Sn NMR spectrum (149.26 MHz, CDCl3) of the crude mixture of the
reaction of formation of 35. . . . . . . . . . . . . . . . . . . . . . . . . . 165
80 POV-Ray image of the molecular structure of
MeSi[CH2Sn(CH2SiMe3)S]3, 35. . . . . . . . . . . . . . . . . . . . . . 166
81 119Sn NMR spectrum (149.26 MHz, CDCl3) of compound 35. . . . . . . 167
82 119Sn NMR spectra (223.85 MHz, CDCl3) of redistribution reactions of
33 and 34. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
6
LIST OF FIGURES
83 Kinetic study of redistribution reactions of 33 and 34 in CDCl3 (Integra-
tion % = f(t)). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
84 A 119Sn NMR spectrum (223.85 MHz, CDCl3) of a solution containing
equimolar amounts of 33 and 34 at day 21. . . . . . . . . . . . . . . . . . 171
85 Cut-out of an 119Sn NMR spectrum (223.85 MHz, CDCl3) showing the
signal for the SnSe2 atom in (C). . . . . . . . . . . . . . . . . . . . . . . 171
86 Cut-out of an 119Sn NMR spectrum (223.85 MHz, CDCl3) showing the
signals for species C+D. . . . . . . . . . . . . . . . . . . . . . . . . . . 172
87 Cut-out of an 119Sn NMR spectrum (223.85 MHz, CDCl3) showing the
signal for the SnS2 atom in (D). . . . . . . . . . . . . . . . . . . . . . . . 172
88 77Se NMR spectrum (114.48 MHz, CDCl3) of a solution containing
equimolar amounts of 33 and 34 (day 21). . . . . . . . . . . . . . . . . . 173
89 119Sn NMR spectra (223.85 MHz, C6D6) of redistribution reactions of 33
and 34. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
90 Kinetic study of redistribution reactions of 33 and 34 in C6D6: (Integration
% = f(t)). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
91 119Sn NMR spectra (223.85 MHz, CDCl3) of redox reactions of 34 with
S8 in 1:1 ratio. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
92 Kinetic study of redox reactions of 34 with S8 in CDCl3: (Integration % =
f(t)). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
93 Calculated Spectral emission characteristics of 33 (B), 34 (A) and the
intermediates (C) and (D): UV (a.u) = f(Energy). . . . . . . . . . . . . . 180
94 Calculated Spectral emission characteristics of the CH2SiMe3-substituted
silastannadamantane theoretical intermediates: UV (a.u) = f(Energy). . . . 180
95 POV-Ray image of the molecular structure of
{[MeSi(CH2)3]SnCl(CH2SiMe3)(µ3-O)SnCl(CH2SiMe3)Sn(µ3-O)(Cl)2
(CH2SiMe3) Sn(Me)2}, 2. . . . . . . . . . . . . . . . . . . . . . . . . . 190
96 119Sn NMR spectrum (149.26 MHz, C6D6) of crude mixture reaction of
compound 1. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
97 POV-Ray image of the molecular structure of Ph3Sn(CH2)2NH2, 1. . . . . 195
98 POV-Ray image of the molecular structure of
Ph3Sn(CH2)2NH2(CH2CMe2OH)2, 2. . . . . . . . . . . . . . . . . . . . 197
99 POV-Ray images of the molecular structure of
[Ph3Sn(CH2)2NH2(CH2CMe2O)2]2Sn, 3. . . . . . . . . . . . . . . . . . 199
7
TABLE OF SCHEMES
Table of Schemes
1 Multicentric organotin-containing compounds as anion, Lewis base as well
as ditopic receptors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2 a) Syntheses methods for obtaining ladder-like tetraorganodistannoxanes. . . 18
2 b) Different A, B and C-types of ladder-type structures. . . . . . . . . . . . 18
3 Syntheses of the organotin derivatives MeSi(CH2SnR(3 –n)Xn)3, (n = 0– 3;
X = I, F, Cl, Br; R = Ph, CH2SiMe3). . . . . . . . . . . . . . . . . . . . . 20
4 Reaction of 4 with one molar equiv of C11H21N2Cl. . . . . . . . . . . . . 39
5 Reaction of 4 with two molar equiv C11H21N2Cl. . . . . . . . . . . . . . 42
6 Reaction of 12 with one molar equiv C11H21N2Cl. . . . . . . . . . . . . . 45
7 Reaction of 4 with one molar equiv NO3PPh4. . . . . . . . . . . . . . . . 47
8 Reaction of 4 with three molar equiv HMPA (1) and six molar equiv HMPA
(2). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
9 Reaction of 6 with four molar equiv HMPA: formation of 18 and 19. . . . 53
10 Reaction of 6 with one molar equiv PPh4Cl. . . . . . . . . . . . . . . . . 59
11 Reaction of 6 with two molar equiv PPh4Cl. . . . . . . . . . . . . . . . . 60
12 Reaction of 7 with one molar equiv NEt4F ·2H2O. . . . . . . . . . . . . . 61
13 Reaction of 5 with three molar equiv AgO(O)CCH3. . . . . . . . . . . . 67
14 Reaction of 9 with one molar equiv PPh4Br. . . . . . . . . . . . . . . . . 73
15 Reaction of 9 with two molar equiv NEt4Br. . . . . . . . . . . . . . . . . 76
16 Syntheses of the tris(organostannylmethyl)stannane derivatives
R’Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R = Ph, R’ = R,
X). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
17 Products of the complexation attempt of the dichloride-substituted com-
pound 3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
18 Complex 8 as a product of the complexation attempt of the dichloride-
substituted compound 3. . . . . . . . . . . . . . . . . . . . . . . . . . . 107
19 Reaction of compound 3 with one molar equiv pyridinium chloride giving
organochloridostannate complex 9 as the only isolated material. . . . . . 109
20 Synthesis of the octanuclear ladder-like oxocluster 26. . . . . . . . . . . 116
21 Synthesis of the tetranuclear ladder-like diorganotin oxocluster 27. . . . . 123
22 Schematic drawing of the solid-state structure of compound 27. . . . . . . 127
23 Synthesis of the tetranuclear ladder-like diorganotin oxocluster 28. . . . . 129
24 Formal interpretation of the solid-state structure of compound 28. . . . . 131
25 Synthesis of the macrocycle 29. . . . . . . . . . . . . . . . . . . . . . . 134
8
TABLE OF SCHEMES
26 Synthesis of the macrocycle 30. . . . . . . . . . . . . . . . . . . . . . . 141
27 Association of two adamantane-type diorganotin oxide moieties A under-
going subsequent ring-opening dimerization giving C. The existence in
solution of these moieties gets support from electrospray ionization mass
spectrometry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
28 Synthesis of the hexanuclear organotin oxo-cluster ladder-like compound
32. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
29 Synthesis of the silastannaadamantane compound 33. . . . . . . . . . . . 156
30 Synthesis of the Se-silastannaadamantane compound 34. . . . . . . . . . 160
31 Synthesis of the S-silastannaadamantane MeSi(CH2SnCH2SiMe3S)3, 35. 165
32 Different intermediate species (A, B, C, and D) formed in course of the
redistribution reaction between 33 and 34 in CDCl3. . . . . . . . . . . . . 168
33 Different intermediate species (A, B, C, and D) formed during the ex-
change reaction between 33 and 34 in C6D6. . . . . . . . . . . . . . . . . 175
34 Different intermediate species (A, B, C, and D) formed during the redox
reaction between 34 with S8 in CDCl3. . . . . . . . . . . . . . . . . . . . 177
35 Possible intermediate (or transition state) involved in the redistribution
reaction between 33 and 34. . . . . . . . . . . . . . . . . . . . . . . . . 179
36 Possible intermediate (or transition state) involved in the redox reaction
between compound 34 and elemental sulfur, S8. . . . . . . . . . . . . . . 179
37 Base hydrolysis as a Synthesis method for obtaining ladder-like tetraor-
gandistannoxanes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
38 Synthesis of the distannoxane derivative 2. . . . . . . . . . . . . . . . . . 188
39 Ditopic complex of sodium fluoride, NaF. . . . . . . . . . . . . . . . . . 192
40 Concept of synthesis of organotin-functionalized cryptand. . . . . . . . . 193
41 Synthesis of Ph3Sn(CH2)2NH2, 1. . . . . . . . . . . . . . . . . . . . . . 194
42 Synthesis of Ph3Sn(CH2)2NH2(CH2CMe2OH)2, 2. . . . . . . . . . . . . 196
43 Synthesis of [Ph3Sn(CH2)2NH2(CH2CMe2O)2]2Sn, 3. . . . . . . . . . . 198
9
LIST OF CHARTS
List of Charts
1 Host-guest concept in chemistry. . . . . . . . . . . . . . . . . . . . . . . 14
2 Different types of diorganotin oxides. . . . . . . . . . . . . . . . . . . . 115
3 The organotin compounds MeSi(CH2SnR(3 –n) Xn)3, 2– 12. . . . . . . . . 204
4 a) The organostannate complexes 13– 19. . . . . . . . . . . . . . . . . . . . 205
4 b) The organostannate complexes 20–25. . . . . . . . . . . . . . . . . . . . 205
5 R'Sn(CH2SnR(3 –n)Xn)3 derivatives 2– 5 and organostannate complexes 6–
9. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
6 a) Organotin oxo clusters 26– 27. . . . . . . . . . . . . . . . . . . . . . . . 207
6 b) Organotin oxo clusters 28– 32. . . . . . . . . . . . . . . . . . . . . . . . 208
7 Sila-stanna-adamantane 33– 35. . . . . . . . . . . . . . . . . . . . . . . 209
8 Double-ladder {[MeSi(MeSnCl)(CH2)3(µ3-O)(MeSnCl)(CH2)3]2O}2, 2. . 210
9 Aminoalkanol organostannane compounds 1– 3. . . . . . . . . . . . . . . 210
10
LIST OF TABLES
List of Tables
1 Selected interatomic distances /Å and angles /◦ in compounds 2, 6, and 9. 38
2 Selected interatomic distances /Å and angles /◦ in compounds 13, 14, and
25. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3 Selected interatomic distances /Å and angles /◦ in compounds 16, 18, and
19. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4 Selected NMR data measured in CDCl3 and CD2Cl2 solutions for the
chloride complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
5 Selected interatomic distances /Å and angles /◦C in compounds 17 and 22. 72
6 Selected interatomic distances /Å and angles /◦C in compounds
23 ·0.5CH2Cl2 and 24. . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
7 Selected NMR data measured in CD2Cl2 and CD3CN solutions of the
bromide complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
8 Selected interatomic distances /Å and angles /◦C in compounds 2 and 4. . 103
9 Summary of 119Sn and 77Se NMR Data and coupling constants for Species
A, B, C, and D presented in the exchange reaction between 33 and 34 in
CDCl3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
11
LIST OF ABBREVIATIONS
List of Abbreviations
General Abbreviations
R Organic group c Concentration
Ar Aryl M Molarity
Ph Phenyl mL Milliliter
Me Methyl t Time
Et Ethyl min Minutes
t-Bu tert-Butyl T Temperature
Cy Cyclohexyl i Ipso-position in aromatic ring
X Halide o Ortho-position in aromatic ring
THF Tetrahydrofuran m Meta-position in aromatic ring
DMSO Dimethyl sulfoxide p Para-position in aromatic ring
Molar equiv Molar equivalent Calcd Calculated
Spectrometry and Spectroscopy Parameters
MS Mass spectrometry MHz Megaherz
ESI Electrospray Ionization s Singulett
m/z Mass per charge d Dublett
NMR Nuclear magnetic resonance t Triplett
ppm Parts per million m Multiplett
δ Chemical shift in ppm dd doublet of doublet
J Coupling constant IR Infrarot
Hz Hertz
X-Ray Diffractometer Analysis
a, b, c Unit cell dimensions Z Number of molecules in the unit cell
Å Angström σ Standard deviation
α , β , γ Unit cell angles µ Absorption coefficient
◦ Degree F(000) number of electrons in the unit cell
V Volume of the unit cell Dc Density
12
1. General Introduction
1.1 Host-Guest Approach in Supramolecular Chemistry
Supramolecular chemistry, as cited by Jean-Marie Lehn in 2002, is “the chemistry involv-
ing two or more molecules held together by non-covalent interactions”.[1] As a matter of
fact, host-guest chemistry is a class of supramolecular chemistry. A simplified graphic
illustrating this statement is presented in Chart 1.[2] It shows the different components
forming a host-guest complex. The host is either an organic molecule containing receptor
sites the binding capacity of which is based on hydrogen bonding (as for instance amide,
pyrrole, hydroxyl groups in enzymes),[2] or it is composed of Lewis-acidic metal centers.[3]
The guests can be neutral molecules, anions or cations.[4,5] These two components form
together the host-guest complex which is held together via forces such as coulomb attrac-
tion, hydrogen bonds, pi−pi stacking, dipole-dipole, and Van der Waals interactions.[6] It is
important to note that the first fundamental proposal of the concept of host-guest chemistry
was presented by Emil Fischer 1894 as “Lock and Key”, in which the Lock is the host and
the Key is the guest.[6] Some examples of characteristic host-guest complexes are shown
in Figure 1.[2,6]
Chart 1. Host-guest concept in chemistry.[2]
13
1. General Introduction
Figure 1. Examples of the most known characteristic host-guest complexes.[2,6]
The global interest in this branch of chemistry is demonstrated by a major increase in
research activities in the last decades, and it is rather progressing till now. This is due to
the potential supramolecular chemistry has for biological applications and catalytic pro-
cesses such as “pollutant sequestration, biomedical and environmental monitoring, anion-
exchange and anion-transport”.[7]
1.2 Organotin Compounds in Host-Guest Chemistry
In connection with what is mentioned above, one field of the host-guest chemistry is
the design of complexes oriented toward the recognition of anions and Lewis bases, in
a general perspective. The first anion receptors were recognised in the early 1950s and
1960s.[3] In fact this affiliate of research found a huge amount of difficulties back in time,
giving the critical technicity degree when managing anion with diver characteristics and
large radii. Although, in the near past decades, this field showed important development
as the appearance of different geometrical receptor molecules with higher affinity and
selectivity. It exhibit interesting abilities in biological processes such as ions-sensing,
small molecules activation as well as chemical catalysis.[3] These type of receptors present
as a Lewis acid binding sites metal centres. Most of these are from the group 12, 13 and 14
elements such as boron, aluminium, tin, indium, silicon, tin and mercury...[8,9] This leads us
to the question: what is the utility of organotin compounds as Lewis-bases receptors? First
of all, back to the fundamentals; the reason is that tin as a metal centre shows considerable
Lewis acidity. As the matter of fact, this character is the most important to bind Lewis-
bases in a stable frame with high affinity aspects. It has to be underlined that the Lewis
acidity can be tremendously increased by variation of the substituents bound to the tin
14
1. General Introduction
atom. Furthermore, cooperative effects can be expected when linking several tin atoms
by organic spacers, giving so-called multidentate or multicentric Lewis acids. The latter
concept was in part developed by Jurkschat and co-workers in the last twenty years. A
sum-up of the most interesting multicentric organotin-containing precursors for binding
of anions and neutral Lewis bases is presented in Scheme 1, in addition to some crystal
structures of multidentate organostannate complexes (Figure 2).[3,8–12]
Scheme 1. Multicentric organotin-containing compounds as anion, Lewis base as well as
ditopic receptors.[3,8–12]
Figure 2. Examples of multidentate organostannate complexes.[3,8–12]
15
1. General Introduction
Another characteristic feature of organotin compounds, also related to supramolecular
chemistry, is their ability for building chalcogeno-clusters that hold potential to integrate
small guest molecules.[13] Especially organotin oxoclusters exhibit a high catalytic ac-
tivity for transesterification reactions, acylation of alcohols,[14] and for polymerisation
processes.[13] Going back to history, an early study of the cluster chemistry of organotin
compounds started in 1921. Lambourne reported the synthesis of the first organotin oxo-
cluster of the types [RSn(O)O2CR]n, n = 3, 6 and [(R’Sn(O)O2CR)2R’Sn(O2CR)3]2; R,
R’ = aryl, alkyl. This was the result of the condensation reactions of alkylstannoic with car-
boxylic acids. However, there has been no evidence of further investigation on the structure
of those clusters in the solid state or in solution.[13] It is worth mentioning that the complex-
ity of working with such compounds in terms of isolation and identification[13,14] explains
the long period of time between the first report in 1921 and the complete characterization
of the compounds in 1985, when R. R. Holmes et al. recognized the first drum structure
with the formula [PhSn(O)O2CC6H11]6.[15] This was the first launch of a novel class of
tin compounds, and after that was the appearance of the ladder type structure, known as
an open drum.[16,17] Scheme 2 gives an overview about synthesis methods for tetraorgan-
odistannoxanes, the backbones of the ladder-like organotin oxoclusters. As the matter of
fact, Jurkschat, Dakternieks and co-workers contributed enormously to the identification
of a variety of organotin oxoclusters, exhibiting ladder-like structures in their skeletons.
Actually, they reported three types of assemblies of this class of compounds (Scheme
2. b)[14] : (i) an A-type double ladder structure such as {[R(Cl)Sn(CH2)3Sn(Cl)R]O}4,
(Z = CH2, X = Cl, R = CH2SiMe3),[18] (ii) a dimeric B-type ladder structure such as
{[(Me3Si)2CH(F)Sn(CH2)3Sn(F)CH(SiMe3)2]O}2, and (iii) a C-type monomer ring struc-
ture such as [(Me3Si)2CH(Cl)Sn(CH2)3Sn(Cl)CH(SiMe3)2]O.[19] Finally, some represen-
tative crystal structures of organotin oxoclusters synthesized in our research group are
presented in Figure 3.[18,20–23]
16
1. General Introduction
Scheme 2 a). Syntheses methods for obtaining ladder-like tetraorganodistannoxanes.
Scheme 2 b). Different A, B and C-types of ladder-type structures.[14,18,19]
17
1. General Introduction
Figure 3. Examples for tetraorganodistannoxanes showing double- and triple-ladder struc-
tures, respectively.[18,20–23]
The main objective of this thesis project was to synthesize tripodal tris(organostannyl-
methyl)silanes of the type MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R =
Ph, CH2SiMe3) and study their complexation behaviour towards anions and neutral
Lewis bases. Furthermore, the potential of selected examples for the formation of well-
defined molecular organotin chalcogeno clusters will be evaluated. Among these, the un-
precedented 18- and 30-nuclear molecular diorganotin oxides [MeSi(CH2SnPhO)3]6 and
[MeSi(CH2SnCH2SiMe3O)3]10, respectively, first examples of organotin chalcogenides
with adamantane-type structures containing both organosilicon and organotin moieties, a
tetraorganodistannoxane double ladder based on a silicon-containing spacer-bridged ditin
compound are reported.
18
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F,
Cl, Br; R = Ph, CH2SiMe3), its Characterization, and
its Complexation Behaviour toward Lewis-Bases
2.1 Syntheses and characterization of
MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl,
Br; R = Ph, CH2SiMe3)
Scheme 3 shows the syntheses of the compounds 2–12.
Scheme 3. Syntheses of the organotin derivatives MeSi(CH2SnR(3 –n)Xn)3, (n = 0– 3; X =
I, F, Cl, Br; R = Ph, CH2SiMe3).
Si
Me
Sn
Sn
Sn
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Si
Me
Sn
Sn
Sn
I
Ph
Ph
Ph
Ph
I
Ph
Ph
I
3 I2,
CH2Cl2
−3 PhI
Si
Me
Sn
Sn
Sn
I
I
Ph
Ph
I
I
Ph
I
I
− 6 PhI
Si
Me
Sn
Sn
Sn
Br
Br
Br
Br
Br
Br
Br
Br
Br
9 Br2,
CH2Cl2
−9 PhBr
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
Si
Me
Sn
Sn
Sn
F
Ph
Ph
Ph
Ph
F
Ph
Ph
F
3 KF,
CH2Cl2/H2O
−3KI
6 AgCl,
CH2Cl2
−6 AgI
6 I2,
CH2Cl2
Si
Me
Sn
Sn
Sn
Br
Br
Ph
Br
Br
Ph
Ph
Br
Br
6 Br2,
CH2Cl2
−6 PhBr
Si
Me
Sn
Sn
Sn
Cl
Ph
Ph
Ph
Ph
Cl
Ph
Ph
Cl
3 AgCl,
CH2Cl2
−3 AgI
3 Me3SiCH2Cl
THF, 55−70°Χ
3 MgClI
C2H4Br2
+Si
Me
Sn
Sn
Sn
CH2SiMe3
Ph
Ph
CH2SiMe3
Ph
Ph
CH2SiMe3
Ph
Ph
3 Mg
Si
Me
Sn
Sn
Sn
CH2SiMe3
I
I
CH2SiMe3 I
I
CH2SiMe3
I
I
6 I2,
CH2Cl2, 0°C
−6 PhI
Si
Me
Sn
Sn
Sn
CH2SiMe3
Cl
Cl
CH2SiMe3
Cl
Cl
CH2SiMe3
Cl
Cl
6 AgCl,
CH2Cl2
−6 AgI
MeSi(CH2Cl)3 + 3 NaSnPh3
THF, −70°Χ −3 NaCl
1
2
3 4
5
6 7
8
9
1011
12
19
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
The reaction of tris(chlormethyl)methylsilane MeSi(CH2Cl)3, 1,[24] with sodiumtriphenyl-
stannide, NaSnPh3, in THF affords tris(tri-phenylstannylmethyl)methylsilane
MeSi(CH2SnPh3)3, 2, as a white solid material in very good yield (Scheme 3).
Compound 2 is recrystallized from hot iso-hexan to give single crystals suitable for X-ray
diffraction analysis. It crystallizes in the monoclinic space group P21/c. Figure 4 shows
the molecular structure and selected interatomic distances and angles are given in Table 1.
Figure 4. General view (POV-Ray) of a molecule of 2 showing 30 % probability displace-
ment ellipsoids and the crystallographic numbering scheme. There are disorders of the
phenyl ring C(11) to C(16) and the phenyl ring C(51) to C(56) with a ratio of 60:40 and
55:45, respectively. Only the Ci carbon atoms of the phenyl substituents are shown for
clarity. Selected interatomic distances and angles are given in Table 1.
The environments at Sn(1), Sn(2) and Sn(3) are distorted tetrahedral with angles vary-
ing between 105.13(9)◦ (C3–Sn3–C81) and 118.66(10)◦ (C2–Sn2–C61). The Sn–C dis-
tances varying from 2.120(7) Å (Sn2–C51) and 2.1687(9) Å (Sn2–C61) are typical for
tetraorganotin compounds.[9,12,23,25] Nevertheless, the most interesting aspect to mention
is the tripod geometry of this novel compound 2. The Si(1)–C(1)–Sn(1), Si(1)–C(2)–Sn(2),
and Si(1)–C(3)–Sn(3) interatomic angles of 117.40(14)◦, 120.29(15)◦, and 120.52(14)◦,
respectively are very near. As well, the interatomic distances Si(1)–C(1) 1.867(3) Å, Si(1)–
C(2) 1.871(3) Å, Si(1)–C(3) 1.866(3) Å, and Si(1)–C(4) 1.860(3) Å are almost equal as
20
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
expected. The same holds for the Sn(1)–C(1) 2.154(3) Å, Sn(2)–C(2) 2.147(3) Å, and
Sn(3)–C(3) 2.132(3) Å distances. The environment at the silicon atom is distorted tetrahe-
dral with almost equal angles varying between 107.96(17)◦ (C4–Si1–C2) and 110.52(14)◦
(C3–Si1–C2) and are comparable to the three angles (Si1–C1–Sn1), (Si1–C2–Sn2), and
(Si1–C3–Sn3).
A 119Sn NMR spectrum (Figure 5) of a solution of compound 2 in CDCl3 shows one singlet
resonance at -89 ppm (1J(119Sn – 13C) = 492 Hz), which is comparable to those reported
for the tetraorganotin compounds (Ph3Sn)2CH2 (δ –79 ppm),[26] (Ph3SnCH2)2SnPh2
(terSn δ –79 ppm),[25] and the structurally alike compound (Ph3Sn)3CH (δ –78 ppm).[12]
However, a comparison with the silicon methylene-bridged organotin compound cyclo-
Me2Sn(CH2SiMe2CH2)2SnMe2 (δ 16 ppm)[9] shows that compound 2 is low-frequency
shifted. This can be explained as a result of the different substituent patterns and the ring
structure of the latter compound.
-88.0 -88.5 -89.0 -89.5 -90.0 -90.5 -91.0 -91.5 -92.0 -92
Chemical Shift (ppm)
-
88
.
28
-
89
.
78
-
89
.
81
-
89
.
87
-
89
.
95
-
90
.
01
-
90
.
05
-
90
.
12
-
91
.
97
Figure 5. 119Sn NMR spectrum (149.26 MHz, CDCl3) of compound 2.
A 29Si NMR spectrum shows a singlet resonance at δ 8.75 ppm (2J(29Si – 117/119Sn)
= 21 Hz). It is slightly different with that reported for the analogous compound cyclo-
Me2Sn(CH2SiMe2CH2)2SnMe2 at δ 5.01 ppm (2J(29Si – 117/119Sn) = 50 Hz).[9] This dif-
ference is the result of slightly different substituent patterns in both compounds. In the
1H NMR spectrum a singlet resonance corresponding to the SiCH3 protons at δ –0.19
ppm and another chemical shift are assigned to the (SiCH2Sn) protons at δ 0.33 ppm
21
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
(2J(1H – 117/119Sn) = 78 Hz). This coupling constant value is close to that reported for
the corresponding protons in cyclo-Me2Sn(CH2SiMe2CH2)2SnMe2 (2J(1H – 117/119Sn) =
69 Hz).[9]
In a 13C NMR spectrum the chemical shift at δ 3.9 ppm (3J(13C – 117/119Sn) =
12 Hz, 1J(13C – 29Si) = 51 Hz) is assigned to the (SiCH3) carbon atom. This chem-
ical shift is close to that reported for the corresponding carbon atom in cyclo-
Me2Sn(CH2SiMe2CH2)2SnMe2 at δ 3.6 ppm (3J(13C – 117/119Sn) = 20 Hz).[9] In addi-
tion to that, we find the singlet resonance referring to the (SiCH2Sn) carbon atom
at δ –1.7 ppm (1J(13C – 117/119Sn) = 262/274 Hz, 1J(13C – 29Si) = 48 Hz). These val-
ues are comparable to those measured for the corresponding carbon atom in cy-
clo-Me2Sn(CH2SiMe2CH2)2SnMe2 at δ –2.5 ppm (1J(13C – 117/119Sn) = 229/240 Hz,
1J(13C – 29Si) = 24 Hz).[9] In the aromatic part, the chemical shifts corresponding to
the carbon atoms Cm at δ 128.4 ppm (3J(13C – 117/119Sn) = 49 Hz), Cp at δ 128.7 ppm
(4J(13C – 117/119Sn) = 10 Hz), Co at δ 136.9 ppm (2J(13C – 117/119Sn) = 37 Hz), and Ci at δ
139.6 ppm (1J(13C – 117/119Sn) = 460/492 Hz), are very close to those reported for the cor-
responding carbon atoms in (SnPh3)3CH, respectively, at δ 128.1 ppm (3J(13C – 117/119Sn)
= 51 Hz), δ 128.5 ppm (4J(13C – 117/119Sn) = 11 Hz), δ 137.2 ppm (2J(13C – 117/119Sn) =
38 Hz), and δ 140.2 ppm (1J(13C – 117/119Sn) = 486/511 Hz).[12] All these data are evi-
dence that the tin atoms in compound 2 are four-coordinated with distorted tetrahedral
geometries, as observed in the solid state. An electrospray ionization mass spectrum (ESI
MS positive mode) shows mass clusters centred at m/z 119.1 (100, Sn+) and 383.0097
C18H15SnO2+ (50, [M – C40H43SiSn2 + 2H2O]), respectively (See Supporting Informa-
tion, Chapter 2, Figures S4- S10).
The treatment of compound 2 with six molar equiv of elemental iodine in
CH2Cl2 produces the iodine-substituted tris(diiodidophenylstannylmethyl)methylsilane
MeSi(CH2SnPhI2)3, 3, in quantitative yield. The latter, once reacted with six mo-
lar equiv of silver chloride in CH2Cl2, gives the organotin dichloride derivative
tris(dichloridophenylstannylmethyl)methylsilane MeSi(CH2SnPhCl2)3, 4, in good yield
(Scheme 3).
Compound 4 is a white solid, as to compound 3 is a yellowish oil. Both compounds show
good solubility in common organic solvents such as CH2Cl2, CHCl3, and CH3CN. A
119Sn NMR spectrum of the diiodido-substituted organotin derivative 3 in CDCl3 (Figure
6) shows a singlet resonance at δ –228 ppm which is high-frequency shifted with respect to
the 119Sn chemical shifts reported for (Ph2I2Sn)3CH (δ –262 ppm[12]) and low-frequency
shifted in comparison to that reported for (Ph2I2Sn)2CH2 (δ –24 ppm[21]). The 119Sn
chemical shift of compound 3 is close to that reported for the similar substituted compound
22
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Ph2SnI2 (δ –245 ppm).[27] A 29Si NMR spectrum displays a singlet resonance at δ 8.87
ppm (2J(29Si – 117/119Sn) = 36 Hz).
-225 -226 -227 -228 -229 -230 -231 -232
Chemical Shift (ppm)
-
22
6.
34
-
22
7.
47
-
22
8.
41
-
22
9.
26
-
23
0.
43
Figure 6. 119Sn NMR spectrum (149.26 MHz, CDCl3) of compound 3.
Moreover, in the 1H NMR spectrum a singlet resonance assigned to the SiCH3 protons
at δ 0.53 ppm is observed in addition to the singlet resonance corresponding to the
(SiCH2Sn) protons at δ 1.71 ppm (2J(1H – 117/119Sn) = 84 Hz). The latter resonance is
considerably low-frequency shifted as compared to that reported for the corresponding
methylene protons in (Ph2I2Sn)2CH2 at δ 2.77 ppm (2J(1H – 117/119Sn) = 65 Hz).[21] A
13C NMR spectrum shows one singlet resonance assigned to the SiCH3 carbon atom
at δ 3.2 ppm (3J(13C – 117/119Sn) = 20 Hz, 1J(13C – 29Si) = 40 Hz). Furthermore, a sin-
glet resonance is observed at δ 11.9 ppm (1J(13C – 117/119Sn) = 259/272 Hz, 1J(13C – 29Si)
= 50 Hz) referring to the SiCH2Sn carbon atom. This 13C NMR chemical shift is very
23
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
close to that reported for the corresponding carbon atom in (Ph2I2Sn)2CH2 δ 12.1 ppm
(1J(13C – 117/119Sn) = 269/280 Hz).[21] In the aromatic part, the chemical shifts correspond-
ing respectively to the carbon atoms Cm at δ 129.1 ppm (3J(13C – 117/119Sn) = 77 Hz), Cp
at δ 130.9 ppm (4J(13C – 117/119Sn) = 21 Hz), Co at δ 134.1 ppm (2J(13C – 117/119Sn) =
60 Hz), and Ci at δ 136.6 ppm (1J(13C – 117/119Sn) = 603 Hz), are very close to those re-
ported for the corresponding carbon atoms in (SnPh3)3CH, respectively, at δ 129.0 ppm
(3J(13C – 117/119Sn) = 88 Hz), δ 131.4 ppm (4J(13C – 117/119Sn) = 19 Hz), δ 135.1 ppm
(2J(13C – 117/119Sn) = 66 Hz), and δ 136.6 ppm (no 1J(13C – 117/119Sn) indicated).[12] Also,
after an investigation with 2D NMR COESY, HSQC, and HMBC (See Supporting Infor-
mation, Chapter 2, Figures S12- S21) compound 3 shows a perfect match with the previous
1D NMR study. A 119Sn NMR spectrum of the organotin dichloride-substituted deriva-
tive 4 in C6D6 (Figure 7) presents a singlet resonance at δ 41 ppm (2J(117/119Sn – 29Si) =
48 Hz), which is high-frequency shifted with respect to the 119Sn chemical shifts of the
similar compounds (Ph2Cl2Sn)CH2 (δ 32 ppm)[12] and (PhCl2SnCH2)2SnCl2 (δ –55.8
and δ –101.3 ppm) in CD3CN.[25] This difference is due to the polarity of the solvent in
which the measurement was done.
24
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
44 43 42 41 40
Chemical Shift (ppm)
41
.
89
Figure 7. 119Sn NMR spectrum (149.26 MHz, C6D6) of compound 4.
A 29Si NMR spectrum shows a singlet resonance at δ 7.5 ppm (1J(29Si – 119/117Sn) =
48 Hz). This signal is slightly high-field shifted from the 29Si chemical shift in cyclo-
Cl2Sn(CH2SiMe2CH2)2SnCl2 at 4.1 ppm.[9] The difference is due to the different substi-
tution pattern of the silicon atoms in the two compounds.
A 1H NMR spectrum of compound 4 displays a singlet resonance assigned to the SiCH3
protons at 0.69 ppm which is comparable to that reported for the corresponding protons
in cyclo-Cl2Sn(CH2SiMe2CH2)2SnCl2 at δ 0.35 ppm.[9] Furthermore, the singlet reso-
nance corresponding to the SiCH2Sn protons is found at δ 1.50 ppm (2J(1H – 117/119Sn)
25
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
= 88 Hz). This resonance is shifted to high frequency as compared to that reported
for the corresponding protons in cyclo-Cl2Sn(CH2SiMe2CH2)2SnCl2 at δ 1.02 ppm
(2J(1H – 117/119Sn) = 49/52 Hz).[9] In a 13C NMR spectrum, one singlet resonance at
δ 3.5 ppm (3J(13C – 117/119Sn) = 22 Hz, 1J(13C – 29Si) = 35 Hz) is observed referring
to the SiCH3 carbon atom. The singlet resonance at δ 11.2 ppm (1J(13C – 117/119Sn)
= 361/376 Hz, 1J(13C – 29Si) = 47 Hz) is assigned to the SiCH2Sn carbon atom. The
latter 13C NMR shift is close to those reported for the corresponding carbon atom in
cyclo-Cl2Sn(CH2SiMe2CH2)2SnCl2 at δ 13.4 ppm (1J(13C – 117/119Sn) = 293/306 Hz,
1J(13C – 29Si) = 44 Hz).[9] However, this shift is low-frequency shifted compared to that re-
ported for the SnCH2Sn carbon in (PhCl2SnCH2)2SnCl2 at δ 34.5 ppm (1J(13C – 117/119Sn)
= 606 Hz).[25] In the aromatic part, the chemical shifts corresponding to the carbon atoms
Cm at δ 129.4 ppm (3J(13C – 117/119Sn) = 85 Hz), Cp at δ 131.4 ppm (4J(13C – 117/119Sn)
= 17 Hz), Co at δ 134.3 ppm (2J(13C – 117/119Sn) = 65 Hz), and Ci at δ 139.7 ppm
(1J(13C – 117/119Sn) = 742/773 Hz), are very close to those reported for the corresponding
carbon atoms in (PhCl2SnCH2)2SnCl2, respectively, at δ 129.6 ppm (3J(13C – 117/119Sn)
=101 Hz), δ 131.4 ppm (4J(13C – 117/119Sn) = 20 Hz), δ 135.3 ppm (2J(13C – 117/119Sn) =
67 Hz), and δ 143 ppm.[25] (See Supporting Information, Chapter 2, Figures S34- S37). All
these information confirm that the tin atoms in compounds 3 and 4 are four-coordinated
in solution. As well, the electrospray ionization mass spectrum (positive mode) shows
for 3 mass clusters centred at m/z 392.1, 721.0 corresponding to I2SnH3O+ (30, [M –
C22H24I4SiSn2 + H+ + H2O]+) and C16H19ISiSn3+ (15, [M – C6H5I5]+), respectively, and
in the negative mode mass clusters centred at m/z 127.3 I– (8, [M – C22H24I5SiSn3]– ),
381.0 I3 – (100, [M – C22H24I3SiSn3]– ), 1450.3017 (C22H25I6OSiSn3 ·1.00[M+OH – ]– +
C22H24I6ClSiSn3 ·0.10[M + Cl – ]– ), and 1560.1988 C22H24I7OSiSn3 – ([M + I]– ) (See
Supporting Information, Chapter 2, Figures S22- S32).
A spectrum of 4, in the positive mode, revealed clusters at m/z 738.7, 766.8694, and
776.8050 fitting to C16H21Cl4SiSn3+ (25, [M – Ph – 2Cl– +H+]+), C21H24Cl3SiSn3+ (100,
[M – Me – 3Cl– +H+]+), and C16H22Cl5SiSn3+, respectively (See Supporting Information,
Chapter 2, Figures S38- S41).
The reaction of compound 2 with three molar equiv of elemental iodine in CH2Cl2 gives
the iodine-substituted tris(iodidophenylstannylmethyl)methylsilane MeSi(CH2SnPh2I)3,
5, in quantitative yield as a slightly yellow oil. The corresponding organotin chloride
MeSi(CH2SnPh2Cl)3, 6 is obtained as a colourless crystalline material through the reaction
of 5 with an excess of AgCl in CH2Cl2. Compound 6 crystallizes in the orthorhombic space
Pna21. Compound 5, once reacted with excess of KF in biphasic mixture CH2Cl2/H2O
for 3 days, gives the tris(fluoridodiphenylstannylmethyl)methylsilane MeSi(CH2SnPh2F)3,
7, as a white insoluble solid in very good yield. Further purification is realized by a re-
26
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
peated wash with acetone, water, and methanol. As to compound 5 and 6, they show good
solubility in CHCl3, CH2Cl2, CH3CN, and acetone (Scheme 3).
The 119Sn NMR spectra of the iodido-substituted derivative 5 and the chlorido-substituted
derivative 6 in CDCl3 exhibit both one intense resonance, respectively, at δ –67
ppm and δ 24 ppm (Figure 8). These shifts are very similar to those reported for
(IPh2Sn)2CH2 (δ –68 ppm)[26] (IPh2Sn2CH2)2SiMe2 (δ –65 ppm),[28] (Ph2ISn)3CH (δ
–70 ppm),[12] (ClPh2Sn)2CH2 (δ 20 ppm),[26] (Ph2ClSnCH2)2SnClPh (terSn δ 20 ppm),
(Ph2ClSnCH2SnClPh2)2CH2 (terSn δ 17 ppm).[25] However, when we compare the 119Sn
chemical shift of 5 to that corresponding in {(CH2)3NMe2}PhISnCH2SnPh3 (δ –92
ppm),[29] we found it high-frequency shifted, as for fc(SiMe2CH2SnIPhCH2SiMe2)2fc
(δ –13 ppm),[11] is low-frequency shifted. As for compound 6, the 119Sn NMR shift
is low-frequency shifted in comparison with that reported for (ClMe2Sn2CH2)2SiMe2
(δ 163 ppm), cyclo-(Me(Cl)Sn(CH2SiMe2CH2)2Sn(Cl)Me (δ 174 ppm),[9] and
fc(SiMe2CH2SnClPhCH2SiMe2)2fc (δ 95 ppm).[11] Nevertheless, this chemical shift
is high-frequency shifted, as in approach with that reported for (Ph2ClSn)3CH (δ –9
ppm).[12] This dissimilarity of the chemical shifts mentioned above is explained by the
variety of the substituent patterns about the tin atoms in these different compounds. All
these information are evidences for the four coordination geometry of the tin atoms in 5
and 6 (Figures 5, 6).
The 29Si NMR spectra of 5 and 6 display both a singlet resonance, respectively, at
8.97 ppm (2J(29Si – 117/119Sn) = 28 Hz) and 8.61 ppm (2J(29Si – 117/119Sn) = 30 Hz)
(See Supporting Information, Chapter 2, Figures S45, S56). These shifts are close to
those reported for (IPh2Sn2CH2)2SiMe2 (δ 6.7 ppm) (2J(29Si – 117/119Sn) = 27 Hz), and
(ClPh2Sn2CH2)2SiMe2 (δ 6.1 ppm) (2J(29Si – 117/119Sn) = 29 Hz).[28] The 1H NMR spec-
tra of the organotin compounds 5 and 6 show for both, as expected, two singlet resonances,
at 0.15 ppm and 0.35 ppm, respectively, referring to the SiCH3 protons, and two singlet
resonances at 0.99 ppm (2J(1H – 117/119Sn) = 80 Hz) and 0.96 ppm (2J(1H – 117/119Sn) =
79 Hz), respectively, referring to the SiCH2Sn protons (See Supporting Information, Chap-
ter 2, Figures S43, S54). These shifts are very similar to those corresponding to the SiCH3
protons in (IPh2Sn2CH2)2SiMe2 (δ 0.21 ppm)[28] and (ClMe2Sn2CH2)2SiMe2 (δ 0.18
ppm).[9] In addition to that, the shifts corresponding to the SiCH2Sn protons in 5 and 6
are very close to those reported for (IPh2Sn2CH2)2SiMe2 (δ 1.03 ppm) (2J(1H – 117/119Sn)
= 78/81 Hz) and (ClPh2Sn2CH2)2SiMe2 (δ 0.79 ppm) (2J(1H – 117/119Sn) = 77/80 Hz).[28]
However, these latter signals are low-frequency shifted, in comparison with those for com-
pounds (IPh2Sn)2CH2 (δ 1.87 ppm) and (ClPh2Sn)2CH2 (δ 1.54 ppm).[26]
In the 13C NMR spectra of 5 and 6, (See Supporting Information, Chapter 2, Fig-
ures S44, S55) the chemical shifts referring to the SiCH3 carbons are, respec-
27
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
tively, 3.76 ppm (3J(13C – 117/119Sn) = 15 Hz) and 3.6 ppm (3J(13C – 117/119Sn) =
15 Hz, 1J(13C – 29Si) = 40 Hz). These are close to those reported for the corre-
sponding carbons in (IPh2Sn2CH2)2SiMe2) (δ 2.5 ppm) (3J(13C – 117/119Sn) = 16 Hz,
1J(13C – 29Si) = 53 Hz)[28] and in cyclo-(Me(Cl)Sn(CH2SiMe2CH2)2Sn(Cl)Me (δ 3.57
ppm) (3J(13C – 117/119Sn) = 26 Hz).[9]
The chemical shifts assigned to the SiCH2Sn carbon atoms of 5 and 6 are, respectively, 4.14
ppm (3J(13C – 117/119Sn) = 23 Hz, 1J(13C – 29Si) = 48 Hz, 1J(13C – 117/119Sn) = 253/264 Hz)
and 4.13 ppm (3J(13C – 117/119Sn) = 21 Hz, 1J(13C – 29Si) = 48 Hz, 1J(13C – 117/119Sn) =
285/296 Hz). These latter chemical shifts are close to those reported for the correspond-
ing carbon atoms in fc(SiMe2CH2SnIPhCH2SiMe2)2fc (δ 4.32 ppm) (1J(13C – 117/119Sn)
=250 Hz) and fc(SiMe2CH2SnIPhCH2SiMe2)2fc (δ 4.8 ppm) (1J(13C – 117/119Sn) =
266/279 Hz).[11] However, these shifts are high-field shifted comparing to those re-
ported for the corresponding carbon atoms in (IPh2Sn2CH2)2SiMe2 (δ 3.5 ppm)
(3J(13C – 117/119Sn) = 27 Hz, 1J(13C – 29Si) = 47 Hz, 1J(13C – 117/119Sn) = 253/267 Hz) and
(ClPh2Sn2CH2)2SiMe2 (δ 3.1 ppm) (1J(13C – 117/119Sn) = 314/318 Hz).[28] In the aromatic
part, the chemical shifts corresponding to the carbon atoms in 5 and 6 are Cm (5: δ 128.8
ppm, 3J(13C – 117/119Sn) = 60 Hz; 6: δ 128.9 ppm, 3J(13C – 117/119Sn) = 63 Hz), Cp (5: δ
129.9 ppm, 4J(13C – 117/119Sn) = 14 Hz; 6: δ 130.1 ppm, 4J(13C – 117/119Sn) = 12 Hz),Co (5:
δ 135.8ppm, 2J(13C – 117/119Sn) = 60 Hz; 6: δ 135.5 ppm, 2J(13C – 117/119Sn) = 61 Hz), and
Ci (5: δ 137.6 ppm, ) 1J(13C – 117/119Sn) = 520/544 Hz; 6: δ 139.2 ppm, 1J(13C – 117/119Sn)
= 564/589 Hz). These values are very close to those reported for the corresponding car-
bon atoms in (IPh2Sn2CH2)2SiMe2, respectively, Cm (δ 128.8 ppm, 3J(13C – 117/119Sn)
= 60 Hz), Cp (δ 129.9) (4J(13C – 117/119Sn) = 13 Hz), Co (δ 135.7) (2J(13C – 117/119Sn) =
49 Hz), and Ci (δ 137.8) (1J(13C – 117/119Sn) = 540 514/Hz) and (ClPh2Sn2CH2)2SiMe2
Cm (δ 128.9) (3J(13C – 117/119Sn) = 61 Hz), Cp (δ 130.1) (4J(13C – 117/119Sn) = 13 Hz), Co
(δ 135.5) (2J(13C – 117/119Sn) = 51 Hz), and Ci (δ 139.4). For the latter, no coupling con-
stant is reported.[28] Furthermore, the ESI mass spectrum (positive mode) of 5 shows mass
clusters centred at m/z 919.2 C39H44NaSiSn3+ (100, [M – Me – 3I– + 4H+ + Na+]+), and
969.2 C12H23I3O2SiSn3+ (100, [M – 5Ph– + 6H+ + Na+ + 2MeOH]+), and in negative
mode one mass cluster at m/z negative mode 127.3 I– (100, [M – C40H33I2SiSn3+]– ) (See
Supporting Information, Chapter 2, Figures S47- S52). As for 6 the ESI MS spectrum
exhibits in negative mode two mass clusters centred at m/z 1044.86 and 1136.79 fitting to
[C40H39Cl4SiSn3]– and [C40H39Cl3ISiSn3]– , respectively (See Supporting Information,
Chapter 2, Figures S58- S63).
28
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
-66.0 -66.5 -67.0 -67.5 -68.0 -68.5
Chemical Shift (ppm)
-
66
.
73
-
66
.
76
-
66
.
82
-
66
.
85
-
66
.
95
-
67
.
04
-
67
.
10
-
67
.
15
2J(119Sn−29Si) = 28 Hz
33 32 31 30 29 28 27 26 25 24 23 22 21 20 19 18
Chemical Shift (ppm)
25
.
34
24
.
69
24
.
03
23
.
37
22
.
72
1J(119Sn−13Ci) = 307 Hz
1J(119Sn−13Ci) = 587 Hz
Figure 8. 119Sn NMR spectra of compound 5 (149.26 MHz, CDCl3) (left) and 6 (223.85
MHz, CDCl3) (right).
Figure 9 shows the molecular structure in the solid state of compound 6. Table 1 contains
selected interatomic distances and angles. Compound 6 crystallizes in the orthorhom-
bic space group Pna21. The Si–C and Sn–C distances are as expected and vary be-
tween 1.8541(52) (Si1–C3) and 1.8675(56) Å (Si1–C2), and 2.1214(48) (Sn2–C3) and
2.1258(48) Å (Sn1–C2), respectively. The Si(1) atom shows a slightly distorted tetra-
hedral environment with C–Si–C angles varying between 109.184(222)◦ (C3–Si1–C4),
and 110.911(27)◦ (C1–Si1–C4). The Si–C–Sn angles are rather similar and vary between
116.764(245)◦ (Si1–C3–Sn2) and 117.522(254)◦ (Si1–C2–Sn1).
29
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Figure 9. General view (POV-Ray) of a molecule of 6 showing 30 % probability displace-
ment ellipsoids and the crystallographic numbering scheme.
Both compounds 2 and 6 show tripod geometry. An essential difference between the struc-
tures of both compounds is the environment about the tin atoms. In compound 6, the Sn(1)
and Sn(2) atoms are [4+1]-coordinated and exhibit a distorted trigonal bipyramidal envi-
ronment. The C(2), C(5), C(11) (at Sn1) and the C(3), C(17), C(23) (at Sn2) atoms occupy
the equatorial, and the Cl(1), Cl(2) (at Sn 1) and Cl(2), Cl(3) (at Sn2) atoms occupy the
axial positions. The geometrical goodness ∆Σ(θ)[22] for Sn(1) is 39.2◦ and for Sn(2) 56.2◦.
The Sn–Cl distances of 3.8027(17) Å (Sn1–Cl2) and 3.4956(17) Å (Sn2–Cl3) are shorter
than the sum of the van der Waals radii, here after referred to as vdW, of tin and chlorine
atoms (3.92 Å).[30] The latter distances are comparable to those reported for the chlorido-
substituted organotin compounds (Ph2ClSn)3CH [3.4639(19) and 3.3125(19) Å][12] and
Me3SiCH2(Cl2)Sn (CH2)3Sn(Cl2)CH2SiMe3 [3.319(5) and 3.510(5) Å].[31] The third tin
atom Sn(3), has a tetrahedral environment. The other Sn–Cl distances are ranging between
2.3831(17) Å and 2.4067(17) Å. These latter are nearly equal to those reported in the tetra-
coordinated triorganotin chloride [PhC(CH3)2CH2]3SnCl [2.395(4) Å] and (Ph2ClSn)3CH
[2.4059(19) and 2.4205(19) Å].[12]
As mentioned earlier the triorganotin fluoride compound 7 is an insoluble polymer, which
is characteristic to such fluorido-substituted compounds.[28] Therefore, there were attempts
of solubilization via functionalization of such compounds via the use of intramolecularly
coordinating built-in moieties, as for example {Me2N(CH2)3}.[29] In our case, the identity
30
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
of 7 is established via elemental analysis, which fits exactly with the proposed molecule of
C40H39F3SiSn3 with one molecule of H2O and one molecule of HF. The ESI mass spectra
(negative mode) of 7 shows two mass clusters centred at m/z 255.2263 SnH2F7 – [80,
(SnF62 – + HF+ H+)]– and 978.9520 C40H39F4SiSn3 – [40, (M + F – )]– (See Supporting
Information, Chapter 2, Figures S65- S70). The complexation behaviour of compound 7
towards fluoride anion will be discussed subsequently.
Treatment of compound 2 with six and nine molar equiv of elemental bromine at −55 ◦C in
CH2Cl2 gave the tris(dibromidophenylstannylmethyl)methylsilane MeSi(CH2SnPhBr2)3,
8, and the tris(tribromidophenylstannylmethyl)methylsilane MeSi(CH2SnBr3)3, 9, respec-
tively. Compounds 8 and 9 were isolated in good (8) and excellent (9) yields as oily yellow
respectively brown crystalline materials. Both compounds show very good solubility in
CH2Cl2, CHCl3, and CH3CN (Scheme 3).
The nonabromido-substituted compound 9 crystallizes in the orthorhombic space group
Pna21. Figure 10 shows its molecular structure. Table 1 contains selected interatomic
distances and angles. The interatomic Si–C distances ranging between 1.869(16) Å (Si1–
C2) and 1.886(16) Å (Si1–C3) are rather similar, as are the Sn–C distances vary between
2.099(14) Å (Sn3–C3) and 2.124(15) Å (Sn1–C1). As expected, the silicon atom has a
slightly distorted tetrahedral environment with C–Si–C angles varying between 107.7(8)◦
(C2–Si1–C1) and 111.8(7)◦ (C2–Si1–C4). The Si(1)–C(1)–Sn(1) 117.3(8)◦, Si(1)–C(2)–
Sn(2) 118.1(8)◦, and Si(1)–C(3)–Sn(3) (118.8(8)◦) are also rather similar and compa-
rable with the corresponding angles in compound 6. The environments about the tin
atoms are distorted tetrahedral, with angles varying between 103.47(8)◦ (Br4–Sn2–Br5)
and 117.5(4)◦ (C2–Sn2–Br6). The Sn–Br bond distances vary between 2.438(2) (Sn3–
Br7) and 2.480(2) Å (Sn1–Br3). These distances are slightly shorter than that reported
in Bromo(1,4,7,10,13,16-hexaoxacyclononadec-18-methyl)diphenylstannane Sn(1)–Br(1)
2.5846(4) Å.[32] A closer inspection of the supramolecular structure of 9 (Figure 11) re-
veals intermolecular interactions between Br(3)· · ·Sn(2) and Br(9)· · ·Sn(1) of 3.987 Å
and 4.007 Å, respectively, both being shorter than the sum of the vdW radii of the atoms
involved (4.12 Å).[30] Remarkably, there are also secondary intermolecular interactions
between Br(2)· · ·Br(5) (3.605 Å), Br(5)· · ·Br(9) (3.686 Å), and Br(6)···Br(7) (3.608 Å).
All these distances are slightly shorter than twice the van der Waals radius of bromine
(3.70 Å).[30]
31
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Figure 10. General view (POV-Ray) of a molecule of 9 showing crystallographic number-
ing scheme.
Figure 11. Polymeric chain of 9 established through Br· · ·Sn and Br· · ·Br intermolecular
interactions (shown with broken lines).
119Sn NMR spectra show for both 8 and 9 singlet resonances at δ –16 ppm (8) and δ –210
ppm (9) indicating tetracoordination of the corresponding tin atoms (Figure 12). The sig-
nal of 8 is slightly high-frequency shifted in comparison with that reported for the similar
32
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
compound (Br2PhSn)2CH2 (δ –33 ppm), and low-frequency shifted when compared to
that corresponding to (BrPh2Sn)2CH2 (δ –0.03).[26] The 119Sn NMR chemical shift of 9
is slightly low-frequency shifted to that reported for MeSnBr3 (δ –165 ppm) and EtSnBr3
(δ –141 ppm).[27] The differences are due to the variance of the environment about the tin
atoms in each compound. Furthermore, the 1H NMR chemical shifts of the methylene pro-
tons in the bromine-substituted compounds 8 and 9 (See Supporting Information, Chapter
2, Figures S71, S84), respectively, at δ 1.57 ppm (2J(1H – 117/119Sn) = 88 Hz) and δ 1.10
ppm (2J(1H – 117/119Sn) = 120/126 Hz) are low-frequency shifted in comparison to those
assigned to the corresponding protons in bromo(1,4,7,10,13,16-hexaoxacyclononadec-18-
methyl)diphenylstannane δ 1.69 ppm (2J(1H – 117/119Sn) = 68/83 Hz),[32] (Br2PhSn)2CH2
(δ 2.33 ppm), and (BrPh2Sn)2CH2 (δ 1.68 ppm).[26] In addition to that, in the 13C
NMR spectra (See Supporting Information, Chapter 2, Figures S72, S85), the shifts
corresponding to the SiCH2Sn carbon atoms in 8 and 9, respectively, at δ 11.85 ppm
(1J(13C – 117/119Sn) = 318/333 Hz) and δ 18.62 ppm (1J(13C – 117/119Sn) = 420 Hz) are
very close to those reported for (Br2PhSn)2CH2 (δ 16.26 ppm) (1J(13C – 117/119Sn) =
359 Hz)[26] and bromo(1,4,7,10,13,16-hexaoxacyclononadec-18-methyl)diphenylstannane
(δ 18.9 ppm) (1J(13C – 117/119Sn) = 503/527 Hz).[32] The 29Si NMR spectra of 8 and
9 (See Supporting Information, Chapter 2, Figures S73, S86), as well, display both a
singlet resonance, respectively, at 7.52 ppm (2J(29Si – 117/119Sn) = 44 Hz) and 6.09 ppm
(2J(29Si – 117/119Sn) = 45 Hz). An ESI mass spectrum (positive mode) of 8 shows one mass
cluster centred at m/z 721.0 that is assigned to C12H20Br2NSiSn3+ (100, [M – 4Br– –
2Ph + CH3CN + H+]+). An ESI mass of 9 shows two mass clusters centred at m/z
356.3 (100, [PhSnBr2H + H+])+ and 725.5 (C4H11Br5NOSn2, 50,[M – MeSiC2H4SnBr4 +
MeOH + CH3CN + H+])+. In the negative mode, for 8 a tin-containing mass cluster centred
at m/z 944.7 (C3H13Br6O2SiSn3 – ,30,[M – Me + 3Ph + H2O + OH– ]– ) and for 9 a mass
cluster centred at m/z 358.8 (SnBr3 – ,100,[M – MeC3H6SiSn2Br6])– were observed (See
Supporting Information, Chapter 2, Figures S75- S82, S88- S93).
33
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
1J(119Sn −13C) = 332 Hz
1J(119Sn−13Ci) = 712 Hz
-13 -14 -15 -16 -17 -18
Chemical Shift (ppm)
-
14
.
13
-
14
.
98
-
15
.
74
-
16
.
44
-
17
.
30
-200 -205 -210 -215
hemical Shift (ppm)
-
21
0.
11
Figure 12. 119Sn NMR spectra of compound 8 (223.85 MHz, C6D6) (left) and 9 (149.26
MHz, CDCl3) (right).
The reaction of the monoiodido-substituted organotin compound 3 with three molar
equiv of trimethylsilylmethylmagnesium chloride in THF gives the tetraorgan-
otin derivative tris[diphenyl(trimethylsilylmethyl)stannylmethyl)methylsilane
MeSi[CH2Sn(CH2SiMe3)Ph2]3, 10. The latter was isolated in good yield
as a slightly yellow oily substance. Further purification was achieved by
several washings with iso-hexane. Furthermore, the treatment of 10 with
six molar equiv of elemental iodine in CH2Cl2 provides the diiodine-
substituted tris(diiodido(trimethylsilylmethyl)stannylmethyl)methylsilane
MeSi[CH2Sn(CH2SiMe3)I2]3, 11. The latter, once reacted with six mo-
34
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
lar equiv of silver chloride in CH2Cl2, gives the organotin dichloride
derivative tris[dichlorido(trimethylsilylmethyl)stannylmethyl]methylsilane
MeSi[CH2Sn(CH2SiMe3)Cl2]3, 12. Compounds 11 and 12 are obtained in very
good yields, respectively, as yellow-orange and colourless solids. Compounds 10– 12
show very good solubility in common organic solvents such as CH2Cl2, CHCl3, and THF
(Scheme 3).
The 119Sn NMR spectra of compounds 10– 12 exhibit each one singlet resonance.
These tin atoms are tetra-coordinated as it is evidenced by their tin chemical shifts
at δ –49 ppm (10), δ –190 ppm (11), and δ 131 ppm (12) (Figure 14), respec-
tively, being similar to those reported for fc(SiMe2CH2SnPh2CH2SiMe2)2fc (δ –51
ppm),[11] [Me2N(CH2)3Ph2SnCH2)2SiMe2 (δ –60 ppm),[28] (I2PhSnCH2)2SiMe2 (δ –
219 ppm),[28] cyclo-Cl2Sn(CH2SiMe2CH2)2SnCl2 (δ 139 ppm).[9] The chemical shifts
of the CH2SiMe3 silicon atoms in the organotin compounds 10 (δ 2.68 ppm), 11
(δ 3.81 ppm), and 12 (δ 2.7 ppm) are low-frequency shifted in comparison to those
reported for the corresponding silicon atoms in (Ph3SnCH2)2SiMe2 (δ 6.2 ppm),
(I2PhSnCH2)2SiMe2 (δ 6.8 ppm),[28] and cyclo-Cl2Sn(CH2SiMe2CH2)2SnCl2 (δ 4.1
ppm).[9] The 1H NMR spectra of the organotin compounds 10–12 (See Support-
ing Information, Chapter 2, Figures S95, S103, S111) show that the signals of the
SiCH2Sn protons in 10 (δ 0.1 ppm, 2J(1H – 117/119Sn) = 72/74 Hz) (see as an ex-
ample Figure 13), 11 (δ 1.72 ppm, 2J(1H – 117/119Sn) = 74 Hz), and 12 (δ 1.2 ppm,
2J(1H – 117/119Sn) = 76 Hz), respectively, are low-frequency shifted in comparison to that
reported for (Ph3SnCH2)2SiMe2 (δ 0.46ppm 2J(1H – 117/119Sn) = 75/77 Hz), and close
to those reported for (I2PhSnCH2)2SiMe2 (δ 1.55 ppm, 2J(1H – 117/119Sn) = 87/90 Hz),
and (Cl2PhSnCH2)2SiMe2 (δ 1.22 ppm, 2J(1H – 117/119Sn) = 89/92 Hz).[28] Furthermore,
the 13C NMR chemical shifts corresponding to the CH2SiMe3 carbon atoms in the
organotin compounds 10 (δ –3.33 ppm, 1J(13C – 117/119Sn) = 255/267 Hz), 11 (δ 14.74
ppm, 1J(13C – 117/119Sn) = 251/263 Hz), and 12 (δ 14.09 ppm, 1J(13C – 117/119Sn) =
328/342 Hz), respectively (See Supporting Information, Chapter 2, Figures S96, S104-
S105, S112- S113), are close to that reported for (Ph3SnCH2)2SiMe2 (δ –3.2 ppm,
1J(13C – 117/119Sn) = 265/277 Hz), and high-frequency shifted in comparison to those re-
ported for (I2PhSnCH2)2SiMe2 (δ 12.6 ppm, 1J(13C – 117/119Sn) = 260/271 Hz),[28] and
cyclo-Cl2Sn(CH2SiMe2CH2)2SnCl2 (δ 13.4 ppm, 1J(13C – 117/119Sn) = 293/306 Hz).[9]
The ESI mass spectra (positive mode) of the organotin compounds 10, 11, and 12, respec-
tively, show mass clusters centred at m/z 1129.3 (10, C43H69Cl2O2Si3Sn3+), 824.9353
C4H12I3SiSn3+ (100, [M – (CH2SiMe3I)3 +H+]+), and 778.929 C8H29Cl5O4Si2Sn3+ (100,
[M – Cl– – 2CH2SiMe3 + 4H2O + H+])+ (See Supporting Information, Chapter 2, Figures
S99- S101, S108- S109, S116- S117).
35
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5 -1.0 -1.5
Chemical Shift (ppm)
3.0227.004.975.9431.88
7.
42
7.
41
7.
38 7
.
36
7.
32
7.
31
7.
30
7.
27
0.
16
0.
10
0.
04
-
0.
14
-
0.
14
-
0.
24
0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0 -0.05 -0.10 -0.15 -0.20 -0.25 -0.30 -0.35 -0.40 -0.45 -0.5
Chemical Shift (ppm)
3.0227.004.975.94
0.
16
0.
10
0.
04
-
0.
03 -0
.
03
-
0.
12
-
0.
14
-
0.
14
-
0.
15
-
0.
15 -0
.
24
2J(1H−117/119Sn) = 72/ 74 Hz
(−CH2−) (−CH2−) (−CH2SiMe3)
−Si(CH3)3
(−CH3)
Complex Pattern: Phenyl groups
4J(1H−117/119Sn) =  7 Hz
Figure 13. 1H NMR spectrum (600.29 MHz, CDCl3) of compound 10.
Figure 14. 119Sn NMR spectra (223.85 MHz, CDCl3) of 10, 11 (149.26 MHz, CDCl3)
and 12 (149.26 MHz, C6D6) (from left to right).
36
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Finally, it’s worth noting that the three tin atoms in each of the silicon-bridged organ-
otin compounds 2– 12 are equivalent on the 1H, 13C, and 119Sn NMR time scale. The
tin atoms are all tetracoordinated, as evidenced by their 119Sn NMR chemical shifts.
From the data at hand it is evident that the structures in solution of the organotin com-
pounds 2– 12 are rather similar to the structures in the solid state as established by single
crystal X-ray diffraction analyses. It is worth mentioning that the 1J(13C – 117/119Sn) and
2J(1H – 117/119Sn) coupling constants for the methylene protons and carbon atoms, respec-
tively, increase with the Lewis acidity of the tin atoms. Thus, the nonabromido-substituted
monoorganotin compound 9 shows the biggest values with 2J(1H – 117/119Sn) = 120/126 Hz
and 1J(13C – 117/119Sn) = 414/430 Hz.
Table 1. Selected interatomic distances /Å and angles /◦ in compounds 2, 6, and 9.
2 6 9
X(1) = Cl(1) X(1) = Br(2)
X(2) = Cl(2) X(2) = Br(5)
X(3) = Cl(3) X(3) = Br(7)
Si(1)–C(1) 1.867(3) 1.8599(68) 1.877(16)
Si(1)–C(2) 1.871(3) 1.8675(56) 1.869(16)
Si(1)–C(3) 1.866(3) 1.8541(52) 1.886(16)
Si(1)–C(4) 1.860(3) 1.8648(49) 1.853(15)
Sn(1)–C(1) 2.154(3)
Sn(1)–C(2) 2.147(3)
Sn(1)–C(3) 2.132(3)
Sn(1)–X(1) 2.3831(17) 2.449(2)
Sn(2)–X(2) 2.3985(15) 2.446(2)
Sn(3)–X(3) 2.4067(17) 2.438(2)
Si(1)–C(1)–Sn(1) 117.40(14) 117.3(8)
Si(1)–C(2)–Sn(2) 120.29(15) 118.1(8)
Si(1)–C(3)–Sn(3) 120.52(14) 118.8(8)
Si(1)–C(2)–Sn(1) 117.522(254)
Si(1)–C(3)–Sn(2) 116.764(245)
Si(1)–C(4)–Sn(3) 116.808(246)
C(2)–Sn(2)–C(61) 118.66(10)
C(3)–Sn(3)–C(81) 105.13(9)
C(2)–Sn(1)–Cl(1) 102.999(156)
C(5)–Sn(1)–Cl(1) 102.866(167)
Br(5)–Sn(2)–Br(4) 103.47(8)
C(2)–Sn(2)–Br(6) 117.5(4)
37
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
2.2 Reactivity of halogen-substituted derivatives
MeSi(CH2SnR(3 – n)Xn)3 (n = 1– 3; X = I, F, Cl,
Br; R = Ph, CH2SiMe3) towards anions and neutral
Lewis-Bases
The complexation behaviour of the silicon-bridged organotin compounds of 4– 7, 9, and
12 with Cl– , CH3COO– , F– , Br– , and HMPA are studied in solution by 119Sn, 19F, 31P,
13C, 1H NMR spectroscopy and ESI mass spectrometry (4– 9, 12). The study in solid state
is exclusive for 4– 7, 9, and 12.
2.2.1 Complexation behaviour of 4 and 12 towards chloride anions
and HMPA, respectively
The ability of the hexachlorido-derivatives 4 and 12 to complex chloride anions (as
imidazolium chloride, C11H21N2Cl) in solution is studied. A 119Sn NMR spectrum
(CH2Cl2/C6D6) at ambient temperature of a solution of 4 in dichloromethane to which
one molar equiv of C11H21N2Cl had been added (Scheme 4) shows an unresolved broad
resonances, which cannot be defined. It indicates chloride exchange being fast on the 119Sn
NMR scale.
Scheme 4. Reaction of 4 with one molar equiv of C11H21N2Cl.
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
4
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph Cl
Cl
C11H21N2Cl, 
CH2Cl2 C11H21N2 2
Cl
Cl
13
1/2 MeSi(CH2SnPhCl2)3+ 1/2
4
From this reaction mixture a crystalline material was isolated and re-crystallized from
dichloromethane/ toluene giving the imidazolium salt of the diorganochloridostannate
complex (C11H21N2)2[MeSi(CH2SnPhCl2)3 · 2Cl], 13 (Scheme 4). Figure 15 shows its
molecular structure and the figure caption contains selected interatomic distances and
angles.
38
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Figure 15. General view (POV–Ray) of a molecule of 13 showing crystallographic
numbering scheme. Only the Ci of the phenyl substituents are shown, Hydrogen atoms
and the N2C11H21+ cations are omitted. Selected interatomic distances (Å): Sn(1)–C(1)
2.113(6), Sn(1)–C(11) 2.161(6), Sn(1)–Cl(1) 2.554(2), Sn(1)–Cl(2) 2.3798(18), Sn(1)–
Cl(3) 2.554(2), Sn(2)–C(2) 2.099(6), Sn(2)–C(21) 2.142(7), Sn(2)–Cl(4) 2.505(2), Sn(2)–
Cl(5) 2.3738(18), Sn(2)–Cl(6) 2.6515(19), Sn(3)–C(3) 2.113(6), Sn(3)–C(31) 2.115(8),
Sn(3)–Cl(6) 2.9217(18), Sn(3)–Cl(7) 2.426(2), Sn(3)–Cl(8) 2.3487(18). Selected inter-
atomic angles (◦): Cl(1)–Sn(1)–Cl(3) 169.68(6), C(1)–Sn(1)–C(11) 125.4(2), C(1)–Sn(1)–
Cl(2) 120.81(18), C(11)–Sn(1)–Cl(2) 113.74(18), Cl(4)–Sn(2)–Cl(6) 170.51(6), C(2)–
Sn(2)–C(21) 127.9(3), C(2)–Sn(2)–Cl(5) 119.11(18), C(21)–Sn(2)–Cl(5) 112.8(2), Cl(6)–
Sn(3)–Cl(7) 172.56(7), C(3)–Sn(3)–C(31) 126.4(3), C(3)–Sn(3)–Cl(8) 120.58(19), C(31)–
Sn(3)–Cl(8) 109.0(2).
Compound 13 crystallizes, as its toluene solvate 13·2C7H8, in the monoclinic space group
P21/n with four molecules in the unit cell. The Sn(1), Sn(2), and Sn(3) centers are each
pentacoordinated and show distorted trigonal bipyramidal environments with Cl(1) and
Cl(3) (at Sn1), Cl(4) and Cl(6) (at Sn2), and Cl(6) and Cl(7) (at Sn3) occupying the axial,
and C(1), C(11) and Cl2 (at Sn1), C(2), C(21) and Cl(5) (at Sn2), and C(3), C(31) and
Cl(8) (at Sn3) occupying the equatorial positions. As it is evident from the geometric
39
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
goodness δΣ(θ)[22] = 91.5◦ for Sn1, 81.1◦ for Sn2, and 66.5◦ for Sn3, the distortion from
the ideal trigonal bipyramid is low for Sn(1) and Sn(2). However, the Sn(3) center can be
seen as [4+1] coordinated with Cl(6) approaching Sn(3) vial the tetrahedral face defined
by C(3), C(31) and Cl(8) at a distance of 2.9217(18) Å which, however, is shorter than
the sum of the van der Waals radii of the tin (2.17 Å) and chlorine (1.75 Å) atoms.[30] As
result of this intramolecular Cl(6)→Sn(3) interaction, the Sn(2)–Cl(6) distance is length-
ened to 2.6515(19) Å. These values (formally) indicate an unsymmetrical chelation of
the chloride anion Cl(6) by the Lewis acidic tin centers Sn(2) and Sn(3). The distances
resemble those reported for the tetraphenylphosphonium organochloridostannate complex
(Ph4P)[HC(SnClPh2)3·Cl] (2.9397(14) and 2.6307(14) Å).[12]
A 119Sn NMR spectrum (poor signal-to-noise ratio as result of low solubility of 13 at
low temperature) of a CD2Cl2 solution of 13 at −80 ◦C showed two broad signals at δ
–49 and δ –151 ppm, respectively. These two resonances are low-frequency shifted in
comparison to the parent compound 4 (δ 41 ppm). This is evidence of the formation
of a chloridostannate complex 13 (C11H21N2)2[MeSi(CH2SnPhCl2)3 · 2Cl] (Scheme 4)
chelating two chloride anions in a bidentate manner. However, in another 119Sn NMR
Spectrum in CD3CN at −30 ◦C, only one broad signal is shown at δ –153 ppm (See
Supporting Information, Chapter 2, Figures S119, S120). This difference is due to the
kinetic lability of such compounds. It is worth noting that despite that the reaction was
with one molar equiv of chloride anion, 4 reacts additionally with another chloride anion to
form a bidentate specie, this is approachable to the complexation behaviour of methylene-
bridged organotin compounds such as (ClPh2Sn)2(CH2)3 and (FPh2Sn)2(CH2)3.[3] This
is related to the geometry of each compound and its Lewis-acidity. This kind of bidentate
complexation is explained also that there are two substituted chloride on each tin atom,
which encourage the formation of the 1: 2 adduct. As for the monosubstituted halido-
orgatin compounds, they, generally, chelate the halide anions in a monodentate manner.[3]
To conclude for complex 13, each tin atom interacts with three chlorine atoms and cannot
be involved in additional intramolecular interaction with a fourth Cl– , they are all satisfied.
A 119Sn NMR spectrum at ambient temperature of a solution of 4 in acetonitrile, to which
two molar equiv of C11H21N2Cl had been added, shows a single resonance at δ –160 ppm,
W1/2 = 255 Hz (Scheme 5).
40
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Scheme 5. Reaction of 4 with two molar equiv C11H21N2Cl.
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
4
2 C11H21N2Cl, 
CH2Cl2
14
2/3 MeSi(CH2SnPhCl2)3+ 1/3
4
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
C11H21N2 3
Cl
Cl Cl
It is low-frequency shifted in comparison to the parent compound 4 (δ 41 ppm) and
proves formation of organochloridostannate species. All tin atoms involved in the equi-
librium shown in Scheme 5 are equivalent on the 119Sn NMR time scale. Even at −80 ◦C
no de-coalescence of the 119Sn NMR signal was observed. From this reaction mixture,
the imidazolium organochloridostannate (C11H21N2)3[MeSi(CH2SnPhCl2)3·3Cl], 14 was
isolated as colourless crystalline material. From an acetonitrile/dichloromethane solution,
14 crystallized in the orthorhombic space group Pna21 with four molecules in the unit
cell. Figure 16 shows the molecular structure and Table 2 contains selected interatomic
distances and angles.
Figure 16. General view (POV-Ray) of a molecule of 14 showing crystallographic num-
bering scheme. Only the Ci of the phenyl substituents are shown, Hydrogen atoms and the
N2C11H21+ cations are omitted.
41
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
The binding mode of 14 show that each tin is substituted with three chlorine atoms, in
which the tin atoms are all pentacoordinated with distorted trigonal bipyramidal environ-
ments. The geometrical goodnesses ∆Σ(θ)[22] of Sn(1), Sn(2), and Sn(3) are 89.4◦, 88.6◦,
and 89.1◦, respectively, with Cl(2), C(1), C(11) (at Sn1), Cl(6), C(2), C(21) (at Sn2), and
Cl(8), C(3), C(31) (at Sn3) occupying the equatorial, and Cl(1), Cl(3) (at Sn1), Cl(4), Cl(5)
(at Sn2), and Cl(7), Cl(9) (at Sn3) occupying the axial positions. There are no intramolec-
ular bridges, as it is the case for similar organochloridostannates.[3,9,12] The Sn–Cl dis-
tances vary between 2.368(5) Å (Sn3–Sn8) and 2.587(4) Å (Sn2–Sn5). These are shorter
than the corresponding Sn–Cl distances in almost all related organochloridostannate com-
pounds, taking as examples (PPh4)2[cyclo-Cl2Sn(CH2SiMe2CH2)2SnCl2 · 3Cl][9] and
(PPh4)2[HC(SnCl2Ph)3 · 2Cl].[12]
Table 2. Selected interatomic distances /Å and angles /◦ in compounds 13, 14, and 25.
13 14 25
X(1) = Cl(6) X(1) = Cl(7)
X(2) = Cl(5)
X(3) = Cl(6) X(3) = Cl(8) X(3) = Cl(7)
Sn(1)–X(1) 2.6515(19) 2.7199(12)
Sn(2)–X(2) 2.587(4)
Sn(3)–X(3) 2.9218(19) 2.368(5) 2.8367(13)
Cl(1)–Sn(1)–Cl(3) 169.68(6) 174.69(18)
Cl(4)–Sn(2)–Cl(6) 170.51(6) 86.17(16)
Cl(7)–Sn(3)–Cl(8) 92.72(7) 86.0(2)
C(31)–Sn(3)–C(3) 126.4(3) 127.1(6) 131.8(3)
Cl(1)–Sn(1)–Cl(2) 90.20(5)
Cl(3)–Sn(2)–Cl(4) 88.26(5)
Cl(5)–Sn(3)–Cl(6) 91.77(6)
A 119Sn NMR spectrum is comparable to that of the crude mixture with a single resonance
at δ –175 ppm. As well, the 1H and 13C NMR spectra of a crystal sample of 14 sup-
port the formation of (C11H21N2)3 [MeSi(CH2SnPhCl2)3·3Cl] (Scheme 5). The 1H NMR
spectrum shows the SiCH3 single resonance at δ 0.58 ppm, displaced to slightly lower
frequency in comparison to that of 4 (δ 0.65 ppm). As to the SiCH2Sn resonance appears
at δ 1.42 ppm, shifting to higher frequency in comparison with the methylene group of 4
(δ 1.18 ppm). As to the resonances referring to the t-Bu groups (δ 1.65 ppm, 54H) and
the CH groups (δ 7.64 ppm 6H, δ 8.63 ppm 3H) of the imidazolium cation, correspond to
three cations of C11H21N2+. In the 13C NMR spectrum, the resonances corresponding to
42
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
SiCH3 at δ 3.67 ppm and SiCH2Sn at δ 27.49 ppm displace to higher frequencies in com-
parison with those of 4, respectively, at δ 3.51 and 11.25 ppm. An ESI-MS spectrum of 14
in the positive mode show three mass clusters centered at m/z 721.0, 739.0, and 1504.3 as-
signed to [M – 3(C11H21N2)+ – 6Cl– – Ph + H2O]+, [M – 3(C11H21N2)+ – 5Cl– + H+]+,
and [M – Cl– – N– + H+ + H2O]+, respectively (See Supporting Information, Chapter 2,
Figures S121- S130).
Despite that the formation of complex 14 is resulted from the reaction of 4 with two molar
equiv of chloride anion, even though, the third tin atom chelate an additional Cl– . This
result is interestingly surprising, giving the affirmation saying that dichlorido-substituted
organotin compounds attempt to complex chloride anion in a bidentate manner and the
third tin atom do not involve in the complexation process.[3] In our case, this result is in
analogy with the previous bidentate specie 13, result of the reaction of 4 with one equiv
molar chloride anion.
In fact, upon the addition of a third molar equiv of imidazolium chloride to a solution
of 13 in acetonitrile, a 119Sn NMR spectrum shows a single resonance at δ –178 ppm
(See Supporting Information, Chapter 2, Figure S132), which proves the formation of 14
in solution. No crystalline material was isolated from this reaction mixture. This finding
confirms that all three tin atoms are satisfied via interactions with a maximum of three
chlorine atoms on each one.
When we compare the complexation behaviour of the phenyl-substituted compound 4 to-
wards chloride anions, to that of the corresponding trimethylsilylmethyl-substituted deriva-
tive 12, we find an interesting result.
A 119Sn spectrum of a solution of 12 in CD3CN at ambient temperature, to which one
molar equiv of C11H21N2Cl had been added, shows a broad resonance at δ –11 ppm,W1/2
= 528 Hz (See Supporting Information, Chapter 2, Figure S231) shifted to lower frequency
in comparison to the parent compound 12 (δ 131 ppm). No crystalline material is isolated
from this reaction mixture. However, a 119Sn spectrum of a solution of 12 in acetonitrile re-
acting with two molar equiv of C11H21N2Cl, shows a broad resonance displaced to a much
lower frequency at δ –48 ppm. At −40 ◦C, the 119Sn spectrum exhibits two broad reso-
nances at δ –122 and -76 ppm, respectively, with integration of 1: 2. (See Supporting Infor-
mation, Chapter 2, Figures S229, S230) This finding is interpreted in terms of the formation
of the organochloridostannate complex (C11H21N2)2 [MeSi(CH2SnCH2SiMe3Cl2)3 · 2Cl]
(25, Scheme 6).
43
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Scheme 6. Reaction of 12 with one molar equiv C11H21N2Cl.
2 C11H21N2Cl, 
CH3CN
12
Si
Me
Sn
Sn
Sn
CH2SiMe3
Cl
Cl
CH2SiMe3
Cl
Cl
CH2SiMe3
Cl
Cl
Si
Me
Sn
Sn
Sn
Cl
Cl
CH2SiMe3
CH2SiMe3
Cl Cl
ClCl
C11H21N2 2
CH2SiMe3
Cl
Cl
25
Colourless single crystals suitable for X-ray diffraction study were obtained from a
solution of CH2Cl2/CH3CN. Complex 25 crystallizes in the triclinic space group P–
1. Figure 17 shows its molecular structure and Table 2 contains selected interatomic
distances and angles. The Sn(1) and Sn(3) centers are intramolecularly bridged via
Cl(7) in a slightly non-symmetrical fashion (Sn1–Cl7) 2.7199(12) Å and (Sn3–Cl7)
2.8367(13) Å. These Sn– distances are comparable to those of 2.7717(8) and 2.8451(8) Å
in (PPh4)[Me2Si(CH2SnClMe2)2 ·Cl].[9] There is a formation of a six membered (Si–C–
Sn–Cl–Sn–C) ring via this Sn–Cl–Sn bridge. The Sn(2) centre binds the second chloride
anion. All tin atoms are pentacoordinated and exhibit distorted-trigonal bipyramidal en-
vironments with geometrical goodness[22] ∆Σ(θ) = 78.8◦ (Sn1), 90.1◦ (Sn2), and 72.9◦
(Sn3). The equatorial positions are occupied by Cl(2), C(1), C(11) at Sn(1), Cl(3), C(2),
C(21) at Sn(2), and Cl(5), C(3), C(31) at Sn(3). The axial positions are occupied by Cl(3),
Cl(7) at Sn(1), Cl(4), Cl(8) at Sn(2), and Cl(6), Cl(7) at Sn(3).
44
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Figure 17. General view (POV-Ray) of a molecule of 25 showing crystallographic num-
bering scheme. Hydrogen atoms and the N2C11H21+ cations are omitted for clarity.
A 1H NMR spectrum of a solution of 25 in CD3CN shows that the Si(CH3)3 resonances
at δ 0.08–0.14 ppm, displaced to slightly lower frequency in comparison to that of 12 (δ
0.06–0.40 ppm), same for the methyl group SiCH3 single resonance which appear at δ 0.47
ppm shifting to a slightly lower frequency comparing to the corresponding methyl group
of 12 (δ 0.59 ppm). As to the CH2SiMe3 and SiCH2Sn resonances appear, respectively
at δ 0.92 and 1.28 ppm, shifting the first to slightly lower frequency and the second to
higher frequency in comparison with the corresponding methylene groups of 12 (δ 0.97
and 1.20 ppm). As to the resonances referring to the t-Bu groups (δ 1.6 ppm, 36H) and
the CH groups (δ 7.56 ppm 4H, δ 8.44 ppm 2H) of the imidazolium cation, correspond
to two cations of C11H21N2+. A 29Si NMR spectrum show two resonances at δ 1.82 and
3.92 ppm corresponding, respectively, to Si(CH3)3 and Si(CH3). These two shift to lower
frequencies comparing to the corresponding silicon atoms in the parent compound 12 (δ
2.7 and 7.29 ppm). An ESI-MS mass spectrum of complex 25 in the negative mode show
one mass cluster centered at m/z 1127.4, assigned to [M – (C11H21N2)+ – 2Cl– – 3H+]–
and in the positive mode one mass cluster centered at m/z 771.1, corresponding to [M –
2(C11H21N2)+ – 7Cl– – CH2SiMe3 + 2H2O + CH3CN]+ (See Supporting Information,
Chapter 2, Figures S227- S228, S233- S236).
Upon addition of a third molar equiv of C11H21N2Cl to the reaction mixture discussed
above, a 119Sn NMR spectrum in CD3CN at ambient temperature shows a broad signal at
δ –77 ppm, W1/2 = 509 Hz (See Supporting Information, Chapter 2, Figure S232), which
45
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
is low-frequency shifted in comparison to the hexachlorido-derivative 12. But this value
is comparable to that of 25. A crystalline material was isolated from this reaction mixture,
showing the same molecular structure of the organotinchloridostannate 25. Giving this
finding, we conclude that compound 12 behaves analogously to the addition of two or three
molar equiv of chloride anions, chelating one in a bidentate manner, while the second one
is complexed to one tin center. The tin centers appear to be satisfied and do not react with
a third molar equiv of Cl– . This behaviour is in contrast to that of compound 14. This is
probably due to a lower Lewis-acidity of the hexachlorido-derivative 12 in comparison
with that of 4. The latter is able binds three chloride anions even upon addition of only
two molar equiv of the chloride anion.
A 119Sn NMR Spectrum of a solution of 4 in CD2Cl2 to which one molar equiv of
NO3PPh4[33] had been added shows a broad resonance at δ –84 ppm (See Supporting
Information, Chapter 2, Figure S136), which is low-frequency shifted when comparing
with the parent compound 4 (δ 41 ppm). This finding is interpreted in terms of the forma-
tion of the 1: 1 adduct (PPh4)[MeSi(CH2SnPhCl2)3 ·NO3] (15, Scheme 7).
Scheme 7. Reaction of 4 with one molar equiv NO3PPh4.
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
4
Si
Me
Sn
Sn
Sn
Ph
Cl
Cl
Ph
Cl
Cl
Ph
Cl
Cl
NO3
15
PPh4
NO3PPh4,
CH2Cl2
Compound 15 was isolated from the reaction mixture as amorphous solid material,
the elemental analysis of which matches perfectly with the Anal. Calcd (%) for
C46H44Cl6NO3PSiSn3: C 42.94, H 3.45, N 1.09, with a (%) of C 43.0, H 3.75, N 0.6.
The identity of 15 gets support by 1H, 13C and 31P NMR spectroscopy and ESI-MS
spectrometry. (See Supporting Information, Chapter 2, Figures S133-S143). A 1H NMR
spectrum exhibits a singlet resonance for the the SiCH2Sn protons at δ 1.56 ppm with
2J(1H – 117/119Sn) = 102 Hz. It is shifted to higher frequency in comparison with the methy-
lene protons of 4 (δ 1.18 ppm, 2J(1H – 117/119Sn) = 84 Hz). As to the complex pattern re-
ferring to the phenyl groups of one PPh4+ cation (20H) combined with those of the novel
complex (15H) appears at δ 7.30–8.03 ppm. A 13C NMR spectrum, displays the resonance
46
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
corresponding to SiCH3 at δ 2.22 ppm which is slightly lower frequency shifted and that
of SiCH2Sn at δ 18.33 ppm, which is displaced to higher frequencies in comparison with
those of 4, respectively, at δ 3.51 and 11.25 ppm. As well, in the aromatic part, there are
the signal resonances referring to Cm (δ 128.5 ppm), Cp (δ 130.08 ppm), Co (δ 135.1
ppm), and Ci (δ 143.7 ppm) of the phenyl groups of complex 15. These latter, except
for Ci, are all slightly lower frequency shifted in comparison with the corresponding 13C
shifts in the parent compound 4 (δ Cm 130.1, Cp 132.1, Co 134.9 ppm). The resonance
for Ci is high frequency shifted (4 δ Ci 139.7 ppm). In addition to those of Cm (δ 130.7
ppm), Cp (δ 117.7 ppm), Co (δ 134.2 ppm), and Ci (δ 135.7 ppm) of the PPh4+ counter
cation. An ESI-MS mass spectrum of complex 15 in the negative mode shows mass clus-
ters centred at m/z 62.7, 1125.3, and 1152.3, which correspond, respectively, to [NO3]– ,
{[(MeSi(CH2SnCl2Ph)3·NO3]– + HPPh2 + H2O}– , and [(C22H25Cl3SiSn3)3+ + 3OH– +
NO3 – + 2H2O + 3CH3CN + MeOH]– .
A 119Sn NMR spectrum at room temperature of a solution of 4 in CDCl3 to which three
molar equiv of HMPA had been added (See Supporting Information, Chapter 2, Figure
S147) shows an rather broad signal at δ –187 ppm (W1/2 = 809 Hz), indicative for a fast
exchange process on the 119Sn NMR time scale. resonance similar chemical shift was
observed for the complex [(Ph2SnCH2)2SnClPh·2HMPA] (δ –186 ppm).[25] It is low
frequency-shifted comparing to that of the parent compound 4 (δ 41 ppm). A 31P NMR
spectrum of the crude reaction mixture at ambient temperature shows a single resonance
at δ 24.3 ppm with no 117/119Sn satellites. The NMR data proof the formation of a HMPA
complex of 4 that is kinetically labile on the corresponding NMR time scales at room
temperature.
From the reaction mixture, the complex MeSi(CH2SnPhCl2·HMPA)3, 16, (Scheme 8) was
isolated as colourless crystalline material that shows good solubility in dichloromethane,
diethyl ether and acetonitrile. Single crystals of 16 suitable for X-ray diffraction analysis
were obtained from its CH2Cl2/CH3CN solution.
47
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Scheme 8. Reaction of 4 with three molar equiv HMPA (1) and six molar equiv HMPA
(2).
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
4
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
P
O
N
N
N
P
O
N
N
N
P
O
NN
N
16
3 HMPA, 
CH2Cl2
(1)
6 HMPA, 
CH2Cl2(2)
Compound 16 crystallizes in the trigonal space group R3c with 6 molecules in the unit
cell. Figure 18 shows its molecular structure and Table 3 contains selected interatomic
distances and angles. Compound 16 shows a propeller-type structure. Both enantiomers
with clockwise and anti-clockwise orientation are present. The three tin atoms are crys-
tallographically equivalent. They are penta-coordinated and exhibit a distorted trigonal
bipyramidal environment with the axial positions being occupied by O(1) and Cl(1) and
the equatorial positions by Cl(2), C(2) and C(3). The distortion is best reflected in the
O(1)–Sn(1)–Cl(1) angle of 173.75(6)◦, which deviates from the ideal angle of 180◦.
The geometrical goodness ∆Σ(θ)[22] is 81.5◦. The Sn(1)–O(1) distance is 2.214(2) Å
is similar to that of the corresponding distances in [o– C6H4(SnClMe2)2·HMPA][8] and
[(Ph2 ClSnCH2)2·HMPA].[34]
The Sn(1)–Cl(1) and Sn(1)–Cl(2) distances are 2.3862(8) and 2.4861(8) Å, respectively.
They are shorter than the corresponding distances in the HMPA complex mentioned
above.[8] Another interesting aspect is the bowl-alike molecular structure of 16, in which
the "bottom" is the methylsilyl head characterising this novel backbone, in addition to that
all Phenyl- and HMPA groups are oriented to the c- axis, in trans-position in regards to the
chlorine atoms. (Figure 19) This is probably due to the innovative tripod geometry of the
novel silicon bridged organotin precursors. As it is reported in literature,[25] the complexa-
tion behaviour of halido di- or tricentric organotin compounds towards HMPA molecules,
show these latter as non-bridging donors. This is approved, also by the chelation manner
described for compound 16.
48
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Figure 18. General view (POV-Ray) of a molecule of 16 showing crystallographic num-
bering scheme for Sn(1). Hydrogen atoms are omitted for clarity.
At −80 ◦C, a 119Sn NMR spectrum of a solution of single crystalline sample of 4 in
CD2Cl2 exhibits four major signals at δ –213.4, -214.7, -216.6, and -217.8 ppm, respec-
tively, with a total integral of 74 %. In addition, there are low intense broad resonances
centered at δ –190 (integral 5.4 %) and δ –253 ppm (partially structured, integral 10.8 %)
(See Supporting Information, Chapter 2, Figure S149). These chemical shifts are are low-
frequency shifted compared with similar compounds; [o– C6H4(SnClMe2)2·HMPA] (δ
–98.9 ppm),[8] [(Ph2SnCH2)2SnClPh·HMPA] (δ –162.9 ppm), but comparable to that for
the complex [(Ph2SnCH2)2SnClPh·2HMPA] (δ –186 ppm).[25] A 31P NMR spectrum
of the same sample at −80 ◦C displays a major resonance at δ 23.53 ppm with an unre-
solved 2J(31P – 117/119Sn) coupling of 181 Hz resembling the chemical shifts reported for
the neutral complexes [o– C6H4(SnClMe2)2·HMPA] (δ 24.5 ppm, 2J(31P – 117/119Sn) =
135 Hz),[8] [(Ph2SnCH2)2SnClPh·HMPA] (δ 25.6 ppm, 2J(31P – 117/119Sn) = 147 Hz), and
[(Ph2SnCH2)2SnClPh·2HMPA] (δ 24.1 ppm, 2J(31P – 117/119Sn) = 148 Hz).[25] Besides,
there are three minor intense resonances (total integral 8.75 % of the major resonance) at δ
23.81, 24.74, and 25.2 ppm, for which no assignment is made. This case is the same for the
49
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
similar compounds mentioned above.[8,25] The identity of 16 is further supported by 1H,
13C, and 31P NMR spectra as well as by ESI-MS mass spectrometry. A 1H NMR spectrum
shows a singlet resonance for the Si(CH3) protons at δ 0.58 ppm, displaced to slightly
lower frequency in comparison to that of 4 (δ 0.65 ppm). The SiCH2Sn methylene protons
show a single resonance at δ 1.53 ppm (2J(1H – 117/119Sn) = 117 Hz) in comparison with
the parent compound 4 (δ 1.18 ppm, 2J(1H – 117/119Sn) = 84 Hz).
The resonance at δ 2.55 ppm, (3J(1H – 31P) = 137 Hz, 54H) refers to the ( – N(CH3)2)3 pro-
tons of three molecules of HMPA. In a 13C NMR spectrum, the resonances corresponding
to SiCH3 at δ 4 ppm and that of SiCH2Sn at δ 18.33 ppm 1J(13C – 117/119Sn) = 519 Hz, are
displaced to higher frequencies in comparison with those of 4, respectively, at δ 3.51 and
11.25 ppm, 1J(13C – 117/119Sn) = 361/376 Hz. As well, in the aromatic part, there are the
signal resonances referring to Cm (δ 128.4 ppm), Cp (δ 129.8 ppm), Co (δ 135.06 ppm),
and Ci (δ 145.3 ppm, 1J(13C – 117/119Sn) = 921/955 Hz) of the phenyl groups of complex
16. These latter, except for Ci, are all slightly lower frequency shifted in comparison with
the corresponding carbon shifts in the parent compound 4 (δ Cm 130.1, Cp 132.1, Co
134.9 ppm). The signal for Ci is high frequency shifted with a bigger coupling constant
in comparison to 4 (Ci δ 139.7 ppm, 1J(13C – 117/119Sn) = 742/773 Hz) (See Supporting
Information, Chapter 2, Figures S144- 149).
In fact, the formation of the 1:3 complex [MeSi(CH2SnCl2Ph)3·3HMPA] is proved by
the observation of one methyl and one methylene groups in the 1H and 13C NMR spectra,
evidence that the three tin centres are all equivalent, so each tin atom is in interaction
with one molecule of HMPA. It is worth noting to underline that the structural change
in 16 imposed on the three tin centres, upon coordination with 3 molecules of HMPT, is
affecting extremely both NMR shifts and coupling constants.
An ESI-MS mass spectrum of complex 16 in the negative mode shows a mass cluster
centred at m/z 810.7 assigned to [C18H23Cl4NO2P2SiSn3]– . In the positive mode, two
mass clusters are shown centered at m/z 180.1 which correspond to [POH(NMe2)3]+ and
740.8 assigned to [C12H42Cl3N6O4P2Sn2]+. The IR spectrum shows P=O absorption band
at νP=O = 1121.9 cm−1 (See Supporting Information, Chapter 2, Figures S150- S157).
Upon addition of 3 more molar equiv of HMPA to the reaction mixture, compound 4
behaves analogously as complex 16 towards HMPA molecules (Scheme 8). A crystalline
material is isolated, which displays the same molecular structure as 16. We can conclude
that there are no formation of 1:6 adduct [MeSi(CH2SnCl2Ph)3·6HMPA]. This is can be
explained with the deficiency of Lewis-acidity of 4.
50
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Figure 19. A POV-Ray image in sticks of a molecule of 16 showing bowl-alike molecular
structure. Hydrogen atoms are omitted for clarity.
2.2.2 Complexation behaviour of 6 towards HMPA molecules and
chloride anions
The complexation behaviour of the trichlorido silicon-bridged triorganotin compound 6
towards HMPA molecules and Chloride anions was also investigated.
A 119Sn NMR spectrum (CDCl3) at ambient temperature of a solution of 6 with a slightly
excess (four molar equiv) of HMPA in CH2Cl2 exhibits an extremely broad signal at
δ –81 ppm (W1/2 = 1675 Hz) due to an exchange process being fast on the NMR time
scale (See Supporting Information, Chapter 2, Figure S168). This resonance is very low-
frequency shifted as compared to that of the parent compound 6 at δ 24 ppm and proofs
the formation of a novel neutral HMPA-containing complex. A 31P NMR spectrum of
the crude mixture at ambient temperature shows a signal resonance at δ 24.64 ppm with
no 117/119Sn satellites due also to the kinetic lability of such compounds. The 1H NMR
spectrum is also an evidence of the formation of a novel complex. The Si(CH3) resonance
at δ 0.23 ppm is displaced to slightly lower frequency in comparison to that of 6 (δ 0.35
ppm). The same holds for the methylene proton SiCH2Sn single resonance which appears
at δ 0.86 ppm (2J(1H – 117/119Sn) = 92 Hz) as compared to that of the parent compound
6 (δ 0.96 ppm, 2J(1H – 117/119Sn) = 79 Hz). The resonance referring to the ( – N(CH3)2)3
protons (δ 2.46 ppm, 2J(1H – 1H) = 9 Hz, 3J(1H – 31P) = 135 Hz, 72H) corresponds to four
molecules of HMPA. In a 13C NMR spectrum, the resonance corresponding to SiCH3 at
51
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
δ 3.44 ppm is slightly low-frequency shifted as to that of SiCH2Sn at δ 9.05 ppm. It is
displaced to higher frequencies in comparison with that of 6, respectively, at δ 3.60, and
4.13 ppm (See Supporting Information, Chapter 2, Figures S164- 166).
A crystalline material was isolated from a solution of CH2Cl2/ CH3CN, suitable for X-Ray
diffraction study. A close inspection of this crystalline material revealed the presence of
two different types of crystals which could be separated manually. They proved to be
the complexes [MeSi(CH2SnPh2)2Cl3CH2SnPh2(HMPA)2], 18, and the HMPA solvate
[MeSi{CH2SnClPh2(HMPA)3}3]·HMPA, 19 (Scheme 9). Figures 20 (18) and 21 (19)
show the molecular structures and Table 3 contains selected interatomic distances and
angles.
Scheme 9. Reaction of 6 with four molar equiv HMPA: formation of 18 and 19.
Si
Me
Sn
Sn
Sn
Cl
Ph
Ph
Ph
Ph
Cl
Ph
Ph
Cl
6
Si
Me
Sn
Sn
SnPh
Cl
Ph
Ph
Ph
Ph
Ph
P
O
N
N
N
18
P
O
N
N
N
Cl
Cl
Si
Me
Sn
Sn
Sn
Cl
Ph
Ph
Ph
Cl
Ph
Ph
Ph
Cl
P
O
N
N
N
P
O
N
N
N
P
O
NN
N
19
· HMPA
4 HMPA, 
CH2Cl2 +1/2 1/2 
 HMPA
Figure 20. General view (POV-Ray) of a molecule of 18 showing the two molecules in
one-unit cell with the crystallographic numbering scheme. Hydrogen atoms are omitted
for clarity and carbon atoms are shown as sticks.
52
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Complex 18 crystallizes in the triclinic space group P–1 with two independent molecules
in the unit cell presenting two enantiomers. The geometric parameters of both molecules
resemble each other and only the structure of the molecule containing Sn(1)–Sn(3) is dis-
cussed in detail. Complex 18 is the product of autoionization. Two HMPA molecules
kick out a chloride anion at Sn(1) and stabilizes a tin cation by two O→Sn interac-
tions at distances of 2.198(6) Å (Sn1–O1) and 2.240(7) Å (Sn1–O2). The Sn(2) and
Sn(3) atoms complex the chloride anion unsymmetrically at Sn(2)–Cl(2) and Sn(3)–Cl(2)
distances of 2.880(2) and 2.814(3) Å, respectively. These bond distances are similar to
those of the corresponding distances reported for [o-C6H4(SnClMe2)2 ·HMPA][8] and
[(Ph2 ClSnCH2)2·HMPA].[34] Crystallographically, there are six non-equivalent tin atoms;
all of these are pentacoordinated, displaying distorted trigonal bipyramidal geometries
with geometrical goodnesses ∆Σ(θ)[22] of 90.9◦ (Sn1), 76.2◦ (Sn2), 76.7◦ (Sn3), 88.0◦
(Sn4), 68.2◦ (Sn5), and 82.8◦ (Sn6). In which, respectively, the axial positions are occu-
pied by O(1) and O(2) at(at Sn1), Cl(1) and Cl(2) (at Sn2), Cl(2) and Cl(3) (at Sn3), O(3)
and O(4) (at Sn4), Cl(4) and Cl(5) (at Sn5), and Cl(5) and Cl(6) (at Sn6). The equatorial
positions are occupied by C2, C5, C11 (at Sn1), C3, C29, C35 (at Sn2), C4, C41, C47 (at
Sn3), C54, C57, C63 (at Sn4), C55, C81, C87 (at Sn5), and C56, C93, C99 (at Sn6). Sn(5)
shows the strongest deviation from the ideal trigonal bipyramidal geometry and can be
seen as [4+1] coordinated with the Cl(5) atom intramolecularly approaching Sn(5) at a
Sn(5)–Cl(5) distance of 2.9073(24) Å. This latter is shorter than 3.92 Å (sum of the vdW
radii of Cl and Sn atoms).[33]
Complex 19 crystallizes in the monoclinic space group P21/n. All Sn atoms are pentacoor-
dinated and show distorted trigonal bipyramidal environments. The geometrical goodness
∆Σ(θ)[22] are equal to 81.9◦ (Sn1), 79.4◦ (Sn2), 79.3◦ (Sn3). The axial positions are occu-
pied by Cl(1), O(1) (at Sn1), Cl(2), O(2) (at Sn2), and Cl(3), O(3) (at Sn3). The equatorial
positions are occupied by C(2), C(5), C(11) (at Sn1), C(3), C(23), C(29) (at Sn2), and
C(4), C(41), C(47) (at Sn3). The distortion is best reflected in the angles of 131.9(2)◦
(C2–Sn1–C52), 133 4(2)◦ (C3–Sn2–C23), and 129.7(2)◦ (C4–Sn3–C41), which deviate
from the ideal angle of 120◦.
There are no intramolecular Sn–Cl–Sn bridges. The Sn–Cl distances are very similar
and vary between (Sn1–Cl1) 2.5018(17) Å and (Sn2–Cl2) 2.521(2) Å. The Sn–O dis-
tances are between 2.301(11) Å (Sn1–O1) and 2.339(5) Å (Sn3–O3). All these values
are comparable to the corresponding distances in [o– C6H4(SnClMe2)2·HMPA][8] and
[(Ph2ClSnCH2)2·HMPA].[34]
53
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Figure 21. General view (POV-Ray) of a molecule of 19 showing the crystallographic
numbering scheme. There is a free HMPA solvent molecule in the unit cell. Hydrogen
atoms are omitted for clarity and carbon atoms are presented in sticks. Only Ci carbons of
the phenyl groups are shown.
54
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Table 3. Selected interatomic distances /Å and angles /◦ in compounds 16, 18, and 19.
16 18 19
Sn(1)–Cl(1) 2.3862(8) 2.5018(17)
Sn(1)–Cl(2) 2.4861 (8)
Sn(1)–O(1) 2.214(2) 2.198(6) 2.301(11)
Sn(1)–O(2) 2.240(7)
Sn(3)–O(3) 2.339(5)
Sn(4)–O(4) 2.245(6)
Sn(2)–Cl(2) 2.880(2) 2.521(2)
Sn(3)–Cl(2) 2.814(3)
Sn(5)–Cl(5) 2.9072(24)
Sn(6)–Cl(5) 2.717(2)
O(1)–Sn(1)–Cl(1) 173.75(6) 173.7(3)
Cl(1)–Sn(1)–C(2) 92.8(19)
Cl(2)–Sn(1)–C(2) 111.21(9)
Cl(2)–Sn(1)–C(3) 117.11(8) 93.0(2)
C(2)–Sn(1)–C(3) 130.96(12)
O(1)–Sn(1)–Cl(2) 84.51(6)
O(1)–Sn(1)–O(2) 178.1(3)
O(1)–Sn(1)–C(2) 88.8(3) 85.1(5)
C(2)–Sn(1)–C(5) 131.9(2)
Cl(1)–Sn(2)–C(3) 91.2(2)
C(3)–Sn(2)–C(23) 133.4(2)
Cl(3)–Sn(3)–C(4) 92.42(19)
O(4)–Sn(4)–C(63) 91.5(3)
C(55)–Sn(5)–C(87) 120.3(3)
At −80 ◦C, the 119Sn NMR spectrum in CD2Cl2 of the solid crystalline material from
which the single crystal of 18 was taken from (the homogeneity of which was, however,
not established by X-ray powder diffraction measurement) exhibits 6 signals referring
each to non-equivalent tin atoms corresponding to more than one species in solution
(compounds 18 + 19) or more with integration ratio from left to right of [1:3:1:1:2], at δ
–104 (1.3) , -133 (3.5) ppm, -170 (broad signal, W1/2 = 920 Hz, 1.4), -185 (broad signal,
W1/2 = 950 Hz, 1.2), -197 (t, 2J(31P – 117/119Sn) = 313 Hz, 1.9), corresponding to two tin
atoms in coordination each with two HMPA molecules (Figure 22). This latter is close
to the corresponding resonances in [(Ph2SnCH2)2SnClPh·HMPA] (δ –162.9 ppm), and
55
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
[(Ph2SnCH2)2SnClPh·2HMPA] (δ –186 ppm).[25] There is also a very low intensity dou-
blet signal at -254 ppm, for which no assignment is made.
The 31P NMR Spectrum of this same crystals sample at −80◦ (Figure 23) displays 2
broad signals with ratio of 4:3, respectively at δ 23.2 and 23.62 ppm. Whereas, no
Sn satellites were defined due to exchange processes being fast even at low temper-
ature. 31P NMR spectrum need to be measured at even lower temperature for bet-
ter interpretation of the complexation behaviour in solution. These latter resonances
are very close to the corresponding phosphorus atoms in the resembling complexes
[o– C6H4(SnClMe2)2·HMPA] (δ 24.5 ppm),[8] [(Ph2SnCH2)2SnClPh·HMPA] (δ 25.6
ppm), and [(Ph2SnCH2)2SnClPh·2HMPA] (δ 24.1 ppm). There are also three low-
intensity signals at δ 22.7, 24.1 and 24.3 ppm like the case of 16, for which no assignments
are made.
An ESI mass spectrum in the negative mode taken from a crystalline
sample shows a mass cluster centred at m/z 1291.1, which is assigned to
[(MeSi(CH2SnCl3Ph2)3·HMPA + PClOH– – (NMe2)3]– and 1046.1 referring to
[(MeSi(CH2SnCl3Ph2)(CH2SnClPh2)(CH2SnO2Ph2)]2 – (See Supporting Information,
Chapter 2, Figures S167, S169- S172). To distinguish between these two compounds in
solution, we need 119Sn and 31P NMR measurements at even lower temperature. Within
the time frame of this PhD, further investigation in solution could not be performed.
-96 -104 -112 -120 -128 -136 -144 -152 -160 -168 -176 -184 -192 -200 -208 -216 -224 -232 -240 -248 -256 -264
Chemical Shift (ppm)
0.221.941.211.473.571.29
-
10
4.
32
-
13
3.
84
-
17
0.
23
-
18
5.
41
-
19
5.
96
-
19
7.
01
-
19
8.
06
-
25
2.
96
-
25
3.
901
3
2
1
2J(119Sn−31P) = 313 Hz
1
Figure 22. 119Sn NMR spectrum of a crystals sample at −80 ◦C (149.26 MHz, CDCl3) of
complexes 18 and 19.
56
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
29.0 28.5 28.0 27.5 27.0 26.5 26.0 25.5 25.0 24.5 24.0 23.5 23.0 22.5 22.0 21.5 21.0
Chemical Shift (ppm)
4.002.92
24
.
32
24
.
17
23
.
62
23
.
24
22
.
77
Figure 23. 31P NMR spectrum of a crystals sample at −80 ◦C (162.02 MHz, CD2Cl2) of
compound 18 + 19.
We want to investigate the complexation behaviour of 6, when we change the type of Lewis-
base, will that be affecting its chelating manner? Therefore, we study the complexation
reaction of this latter toward chloride anions.
A 119Sn NMR Spectrum of a solution containing 6 and one molar equiv of [PPh4]Cl in
CD2Cl2 shows a broad resonance at δ –77 ppm, W1/2 = 980 Hz (See Supporting Informa-
tion, Chapter 2, Figure S178), which is very low-frequency shifted when comparing with
the parent compound 6 (δ 24 ppm).
At −80 ◦C, there are two broad signals at δ –52 ppm (integral 2) and δ –87 ppm (integral
1), respectively. These two resonances are very low frequency shifted in comparison to the
parent compound 6 (δ 24 ppm). This is evidence of the formation of the 1:1 chloridostan-
nate complex (PPh4)[MeSi(CH2SnPh2Cl)3·Cl], 20 (Scheme 10) in which two tin centres
chelate one chloride anion in a bidentate manner (Table 4).
57
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Scheme 10. Reaction of 6 with one molar equiv PPh4Cl.
Si
Me
Sn
Sn
Sn
Cl
Ph
Ph
Ph
Ph
Cl
Ph
Ph
Cl
6
Si
Me
Sn
Sn
Sn
Cl
Ph
Ph
Ph
Ph
Cl
Ph Cl
Ph
PPh4Cl,
CH2Cl2 PPh4 Cl
20
This view is also supported by 1H, 13C and 29Si NMR spectroscopy and ESI-MS spec-
trometry. A 1H NMR spectrum exhibits the SiCH2Sn resonance appearing at δ 0.92 ppm
with 2J(1H – 117/119Sn) = 98 Hz, and that referring to the SiCH3 resonance at δ 0.3 ppm,
shifting both to lower frequency in comparison to the corresponding proton resonances of
6 (δ 0.36, 0.96 ppm, 2J(1H – 117/119Sn) = 84 Hz). As to the complex pattern referring to the
phenyl groups of one PPh4+ cation (20H) combined with those of the novel complex (30H)
appears at δ 7.24-8.01 ppm. A 13C NMR spectrum, displays the resonance corresponding
to SiCH3 at δ 2.96 ppm which is slightly lower frequency shifted and that of SiCH2Sn
at δ 12.05 ppm, which is displaced to higher frequencies in comparison with those of 6,
respectively, at δ 3.6 and 4.13 ppm. As well, in the aromatic part, there are the resonances
referring to Cm (δ 127.9 ppm), Cp (δ 128.6 ppm), these two are slightly lower frequency
shifted in comparison with the corresponding carbon shifts in the parent compound 6 (δ
Cm 128.9, Cp 130.1). As for the resonances of Co (δ 136.56 ppm) and Ci (δ 143.7 ppm)
are high-frequency shifted regarding that of the parent compound 6 (Co 135.5, Ci 139.2
ppm). In addition to those of Cp (δ 117.2 ppm), Cm (δ 130.6 ppm), Co (δ 134.1 ppm),
and Ci (δ 135.7 ppm) of the PPh4+ counter cation. An ESI-MS mass spectrum of complex
20 in the negative mode show a mass cluster centred at m/z 1026.7902 which corresponds
to [M – PPh4+ – Cl– + OH – ]– (See Supporting Information, Chapter2, Figures S175-
S181).
A 119Sn NMR spectrum at ambient temperature in CD2Cl2 the previous reaction mixture
to which a second molar equivalent of [PPh4]Cl had been added, shows an extremely
broad signal at δ –109 ppm (W1/2 = 957 Hz). This resonance is low-frequency shifted with
respect to the parent compound 6 (δ 24 ppm) and the chloridostannate complex 20 (δ –77
ppm) (Table 4).
58
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Table 4. Selected NMR data measured in CDCl3 and CD2Cl2 solutions for the chloride
complexes.
δ 13C(CH2) 1H(CH2) 119Sn(RT) 119Sn(−80 ◦C)
CD2Cl2
20 12.05 0.92 -77 -52, -87
21 14.21 0.97 -109 —
Scheme 11. Reaction of 6 with two molar equiv PPh4Cl.
Si
Me
Sn
Sn
Sn
Cl
Ph
Ph
Ph
Ph
Cl
Ph
Ph
Cl
6
2 PPh4Cl, 
CH2Cl2 Si
Me
Sn
Sn
Sn
Cl
Ph
Ph
Ph
Ph
Cl
Ph
Cl
2
Ph
Cl
Cl
21
PPh4
This finding is interpreted with caution to the formation of the chloridostannate complex
(PPh4)2[MeSi(CH2SnPh2Cl)3·2Cl], 21 (Scheme 11). In addition, there are three low in-
tense signals at –252, –134, and –89 ppm, for which no assignment is made. Further exper-
imental support for the formation of 21 stems from the 13C, and 29Si NMR spectroscopy
and ESI-MS spectrometry. A 13C NMR spectrum displays a resonance corresponding to
SiCH3 at δ 3.62 ppm and that of SiCH2Sn at δ 14.21 ppm, which are both displaced to
higher frequencies in comparison with those of 20, respectively, at δ 2.96 and 12.05 ppm,
and 6 at δ 3.6 and 4.13 ppm. A 29Si NMR spectrum shows a resonance signal at δ 5.53
ppm, shifting to lower frequency regarding to that of 6 (δ 8.61 ppm). An ESI-MS mass
spectrum of complex 21 in the positive mode shows two mass clusters centred at m/z
339.2 and 919.2 which correspond to [PPh4]+ and [M – 2PPh4+ – 2Cl – – CH3 + H+]+,
respectively. No tin-containing mass cluster is observed in an ESI-MS spectrum in the
negative mode (See Supporting Information, Chapter 2, Figures S183- S190).
59
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
2.2.3 Complexation behaviour of 7 towards fluoride anions
The triorganofluorido tin compound 7 appears to be almost insoluble in all organic solvents.
However, upon addition of one molar equiv of NEt4F·2H2O in CH3CN, the solution
becomes clear. A 119Sn NMR Spectrum in CD3CN at ambient temperature shows a very
broad resonance at δ –188 ppm (W1/2 = 2276 Hz). A 19F NMR spectrum of the same
solution displays four unresolved resonances between δ –161 and -82 ppm. Even at −80 ◦C,
there are still unresolved broad signals appearing in both 119Sn and 19F NMR spectra (See
Supporting Information, Chapter 2, Figures S192, 193). This can be explained due to
the inter- and/or intramolecular exchange of the bridging and terminal fluorine atoms in
a fluoridostannate complex, which still remains rapid on the NMR time scale even at
low temperature. An ESI MS(negative mode) shows a mass cluster centred at m/z 979.2
which corresponds to the fluoridostannate anion [MeSi(CH2SnFPh2)3·F]– . It proves the
formation of the 1:1 adduct in solution (See Supporting Information Figures S.202, S203).
Single crystals of fluoridostannate complex (NEt4)2[{MeSi(CH2SnFPh2)3}2·2F] 22
(Scheme 12) were isolated from the reaction mixture by slow evaporation of a
dichloromethane/diethyl ether solution at room temperature. Complex 22 crystallizes in
monoclinic space group P21/n. This crystalline material is poorly soluble in organic sol-
vents which prevents detailed NMR spectroscopic studies in solution. Figure 24 shows the
molecular structure of 22. Table 5 contains selected interatomic distances and angles.
Scheme 12. Reaction of 7 with one molar equiv NEt4F ·2H2O.
Si
Me
Sn
Sn
Sn
Si
Me
Sn
Sn
Sn
F
F
F
F
Ph
F
Ph
Ph
Ph
F
F
PhPh
F
Ph Ph
Ph
Ph
Ph
Ph
NEt4 2
 2 NEt4F. 2 H2O,
 CH3CN2 Si
Me
Sn
Sn
Sn
F
Ph
Ph
Ph
Ph
F
Ph
Ph
F
7 22
+ H2O4
60
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Figure 24. General view (POV-Ray) of a molecule of 22 showing the crystallographic
numbering scheme. Counter cations NEt4+ and hydrogen atoms are omitted for clarity.
Carbon atoms are presented in sticks.
Compound 22 is a centrosymmetric head-to-tail dimer that is realized via unsymmet-
rical Sn(1)–F(1)–Sn(3A) bridges at Sn–F distances of 2.166(4) and 2.226(4) Å. These
distances are comparable to those reported for the organofluorido stannate complexes
NEt4[CH2(SnXPh2)2·F] (X = F, Br, I), ranging between 2.204(2) and 2.274(5) Å,[35] and
for [o– C6H4(SnClMe2)2·F][K·C20H24O6] 2.204(2) and 2.274(5) Å.[8]
The Sn(2)–F(2) (2.032(4) Å) and Sn(3)–F(3) (2.032(4) Å) distances involving ter-
minal fluorine atoms are shorter than the Sn(1)–F(4) (2.172(4) Å) and Sn(2)–F(4)
(2.258(4) Å) distances involving bridging fluorine atoms. This is similar as reported for
[(Ph2FSnCH2)2SnFPh·F][C12H24O·K], with Sn–F distances ranging between 2.02(4) and
2.342(4) Å.[25]
The dimer is composed of two six-membred rings (Sn1–F4–Sn2–C2–Si1–C1) and (Sn1A–
F4A–Sn2A–C2A–Si1A–C1A) and one 12-membred ring (Sn1–C1–Si1–C3–Sn3–F1A–
Sn1A–C1A–Si1A–C3A–Sn3A–F1). There is a central cavity with a volume of 104 Å3,
holding potential for the inclusion of small guest molecules. However, so far attempts at
obtaining host-guest complexes based on 22 failed. All tin atoms are pentacoordinated and
61
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
exhibit distorted trigonal-bipyramidal geometries [geometrical goodness ∆Σ(θ)[22] 90.1◦
(Sn1), 79.8◦ (Sn2), 81.8◦ (Sn3)]. The axial positions are occupied by F1, F4 (at Sn1), F2,
F4 (at Sn2), F1A, F3 (at Sn3). The equatorial positions are occupied by C1, C11, C21 (at
Sn1), C2, C31, C41 (at Sn2), C3, C51, C61 (at Sn3). To conclude, the molecular structure
of 22 in solid stay, is evidence of the formation of 1:1 anionic adduct, as a dimer structure.
A 119Sn NMR spectrum at room temperature of a solution of 7 in CH3CN to which two
mole equiv. of NEt4F·2H2O had been added exhibits three very broad resonances at δ
–220 ppm (W1/2 = 530 Hz) (integration: 1), -213 ppm (W1/2 = 430 Hz) (integration: 1), and
-205 ppm (W1/2 = 440 Hz) (integration: 1) (See Supporting Information; Chapter 2, Figure
S195). The corresponding 19F spectrum (Figure 25) displays four intense resonances at δ
–162, -158, -142, and -129 ppm, with integral ratio of 1:1:1:1. Both the number of signals
and the coupling patterns are evidences of the formation of the 1:1 fluoride adduct 22 in so-
lution. In the 119Sn NMR spectrum, there are two terminal Sn1 at δ –220 ppm and -213 and
one bridging Sn2 at δ –205 ppm. With caution, we assign the two latter resonances, with the
lower-shifted frequencies to the terminal fluorine atoms F1 and F4, in which, respectively,
1J(19F1 – 117/119Sn1) = 1939/2018 Hz, with a satellite-to-signal-to-satellite ratio of approxi-
mately [10:80:10], and 1J(19F4 – 117/119Sn1) = 2010 Hz with a satellite-to-signal-to-satellite
ratio of approximately [6:88:6]. The signal at δ –142 ppm refers to the bridging fluorine
atoms F2, with 1J(19F2 – 117/119Sn) = 1930 Hz, with a satellite-to-signal-to-satellite ratio
of approximately [8:84:8], and that at δ –129 ppm refers to the bridging fluorine atoms F3.
This latter is too broad to enable observation of 1J(19F – 117/119Sn) (Figures 25, 26). These
NMR resonance shifts and their coupling constants are comparable to those reported for
[(Ph2FaSn2CH2)2Sn1FbPh·Fb][Bu4N]+ at δ –101 ppm [1J(19Fb – 117/119Sn1) = 1174/1224,
1J(19Fb – 117/119Sn2) = 573 Hz] and -182 ppm [1J(19Fb – 117/119Sn1) = 2163 Hz] and in
[(Ph2FaSn2CH2Sn1FbPh)2 CH2·2Fc][Bu4N]+ ]+ at δ –122 ppm [1J (19Fb – 117/119Sn) =
1171 Hz], -145 ppm [1J (19Fc – 117/119Sn1) = 1826 Hz], and -151 ppm [1J (19Fa – 117/119Sn2)
= 1906 Hz]. The Fa and Fb are assigned to the terminal and bridging fluorine atoms respec-
tively, and Fc are the chelated fluorine atoms.[28]
62
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
-124 -126 -128 -130 -132 -134 -136 -138 -140 -142 -144 -146 -148 -150 -152 -154 -156 -158 -160 -162 -164 -166 -168 -170
Chemical Shift (ppm)
2.001.461.05
-
12
9.
20
-
14
0.
78
-
14
2.
51
-
14
4.
23
-
15
4.
06
-
15
7.
10
-
15
8.
87
-
16
0.
18
-
16
0.
23
-
16
0.
72
-
16
1.
96
-
16
3.
68
-
16
3.
74
1
1
1
1
Figure 25. 19F NMR spectrum (564.84 MHz, CD3CN) at ambient temperature of the
mixture containing 7 and two molar equiv of NEt4F ·2H2O.
Figure 26. The dianionic fluoridostannate 22, presenting the different terminal and bridg-
ing tin and fluorine atoms.
An ESI-MS spectrum (negative mode) of a crystals sample reveals a 20 % mass cluster cen-
tred at m/z 979.2, fitting perfectly to the species [MeSi(CH2SnFPh2)3·F]– (See Supporting
Information, Chapter 2, Figures S202, S203).
63
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Addition of a third mole equivalent of NEt4F·2H2O to 7 in CH3CN presents also a clear
solution. A 19F NMR spectrum of this solution at ambient temperature in CD3CN is ev-
idence of the formation of two different species in solution (Figure 27), one with major
intensity (94 %) presented with three broad signals of integral ratio 2:2:1, respectively,
at δ –158 ppm [nJ (19F – 117/119Sn) = 2013 Hz] with a satellite-to-signal-to-satellite ra-
tio of approximately [8:84:8], -142 ppm [nJ (19F – 117/119Sn) = 1899 Hz] with a satellite-
to-signal-to-satellite ratio of approximately [9:82:9], and -129 ppm [nJ (19F – 117/119Sn)
= 1153 Hz] satellite-to-signal-to-satellite ratio of approximately [16:68:16]. The sec-
ond species is present in low intensity (6 %), with four resonances of integral ratio
3:1:2:2, respectively, at δ –162 ppm [nJ (19F – 117/119Sn) = 1942/2029 Hz] with a satellite-
to-signal-to-satellite ratio of approximately [8:84:8], -154 ppm [nJ (19F – 117/119Sn) =
1506/1585 Hz] with a satellite-to-signal-to-satellite ratio of approximately [8:84:8], -
140 ppm [nJ (19F – 117/119Sn) = 2334/2373 Hz] satellite-to-signal-to-satellite ratio of ap-
proximately [8:84:8], and -127 ppm [nJ (19F – 117/119Sn) = 2182/2214 Hz, nJ(19F – 19F) =
116 Hz], satellite-to-signal-to-satellite ratio of approximately [8:84:8].
-112 -114 -116 -118 -120 -122 -124 -126 -128 -130 -132 -134 -136 -138 -140 -142 -144 -146 -148 -150 -152 -154 -156 -158 -160 -162 -164
Chemical Shift (ppm)
0.951.000.47
-
12
2.
86
-
12
2.
90
-
12
5.
11
-
12
6.
99
-
12
7.
08
-
12
7.
20 -
12
8.
14
-
12
9.
28
-
13
0.
35
-
13
7.
64
-
13
7.
67
-
13
7.
73
-
13
7.
76
-
13
9.
77 -1
39
.
80
-
14
0.
72
-
14
1.
85
-
14
1.
91
-
14
1.
93
-
14
2.
36
-
14
4.
04
-
15
2.
67
-
15
2.
73
-
15
4.
06
-
15
5.
38
-
15
5.
45
-
15
6.
78
-
15
8.
54
-
16
0.
01
-
16
0.
09
-
16
0.
31
-
16
1.
79
-
16
3.
50
-
16
3.
58
11
0.5
3
1
2
2
Figure 27. 19F NMR spectrum (564.84 MHz, CD3CN) at ambient temperature of a mixture
containing 7 and three molar equiv of NET4F ·2H2O (Integration ratios of the major
intensities resonances are written in red and that of the minor intensities with green).
64
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
-184 -192 -200 -208 -216 -224 -232 -240 -248 -256 -264 -272 -280 -288 -296 -304 -312 -320 -328 -336 -344 -352 -360 -368 -376 -384 -392
Chemical Shift (ppm)
0.020.952.00
-
20
4.
95
-
21
0.
28
-
21
3.
74
-
21
9.
39
-
26
1.
50
-
27
0.
27
-
27
8.
74
-
34
8.
93
1
2
Figure 28. 119Sn NMR spectrum (223.85 MHz, CD3CN) at ambient temperature of com-
pound 7 to which three molar equiv of NEt4F ·2H2O had been added.
The 119Sn NMR of this crude mixture at ambient temperature in CD3CN exhibits two
signal resonances with integration ratio of 2:1, corresponding respectively, to one doublet
of doublets at δ –211 ppm and one triplet at δ –270 ppm (W1/2 = 1983 Hz). (Figure 28)
Most likely the lower-frequency shifted resonance corresponds to terminal tin atoms as to
the other is corresponding to bridging tin atoms, this statement is known in literature.[25,28]
The rather broad signals in both the 19F and 119Sn NMR spectra might be the result of
exchange between bridging and terminal fluorine atoms. Single crystals suitable for X-
ray diffraction study were isolated. These show the same molecular structure as 22 and
similar structure, as the crude mixture in solution (See Supporting Information, Chapter 2,
Figures S200, S201). An ESI-MS spectrum (negative mode) of a crystal sample reveals a
low intensity mass cluster centered at m/z 979.2, fitting perfectly to the monomer anionic
specie [MeSi(CH2SnFPh2)3·F]– (See Supporting Information, Chapter 2, Figures S202,
S203).
Finally, we can conclude, that the fluoridostannate 22 does not behave analogously in
solution and solid state, giving that two different species are present in solution. No one
is referring to the molecular structure found in solid state. However, the dianionic dimeric
form proposed by the molecular structure of 22 seems to be the most stable one. Even upon
addition of two respectively three molar equiv of F– , crystals of 22 are isolated. There
65
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
is always a formation of 1:1 anionic adduct in the solid state. Poor solubility precluded
detailed NMR spectroscopic studies at variable temperature.
2.2.4 Complexation behaviour of 5 towards acetate anions
A 119Sn NMR spectrum of the iodido-substituted triorganotin compound 5 in C6D6 to
which three molar equiv of AgO(O)CCH3 had been added shows six broad signals at δ
–218, -204, -171, -167, -91, and -44 ppm, respectively (See Supporting Information, Chap-
ter 2, Figure S158). This indicates a fast exchange process. The acetate triorganostannate
complex 17 {MeSi[CH2Sn(OCOCH3)Ph2]3}2 was isolated from the corresponding solu-
tion in diethyl ether/CH2Cl2 as single-crystalline material suitable for X-ray diffraction
analysis (Scheme 13, Figure 29).
Scheme 13. Reaction of 5 with three molar equiv AgO(O)CCH3.
Si
Me
Sn
Sn
Sn
O
O
Ph
Ph
Ph
Ph
O
O
O
Ph
O
Ph
Si Me
Sn
Sn
Sn
O
O
Ph
Ph
Ph
Ph
O
O
O
Ph
O
Ph
Si
Me
Sn
Sn
Sn
I
Ph
Ph
Ph
Ph
I
Ph
Ph
I
6 AgCH3COO
CH2Cl2
 6 AgI
2
5 17
A 119Sn NMR spectrum of 17 in CDCl3 (Figure 30) shows three single resonances at
δ –91(2 Sn1’), –90 (2 Sn1), these two resonances are too broad to enable observation
of 4J(119Sn – 117Sn) and –40 ppm (4J(119Sn2 – 117/119Sn1 /Sn1’) = 220 Hz, 2 Sn2), which
are low respectively high frequency-shifted as compared to the parent compound 5 (δ
–67 ppm). Most likely, the signal at –40 ppm corresponds to the two Sn2 atoms while
the signals at δ –91 and –90 ppm belong to the Sn1 and Sn1’ atoms (Figure 31). These
NMR shifts are high frequency-shifted in comparison to the corresponding resonances
in HC[Sn(OAc)Ph2]3 (δ –206 ppm)[12] and H2C[Sn2(OAc)3]2 (δ –540 ppm).[26] An IR
spectrum shows an absorption stretch bands corresponding to the C –– O group at νC=O =
1539 cm−1, and C – O groups at νC−O = 1428, 1018 cm−1 (Figure 32).
66
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Figure 29. General view (POV-Ray) of a molecule of 17 showing the crystallographic
numbering scheme. Hydrogen atoms are omitted for clarity. Carbon atoms are presented
in sticks, only Ci of the phenyl groups are shown.
Figure 30. 119Sn NMR spectrum of crystals sample of 17 at room temperature (400.25
MHz, CDCl3).
67
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Figure 31. The acetate triorganostannate 17, presenting the different tin atoms Sn1,
Sn1'and Sn2 atoms of the eight- and 16-membred rings in the skeleton.
Figure 32. IR spectrum of acetate complex 17, in which the C –– O absorption stretch and
the C – O stretching bands.
68
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
An ESI-MS mass spectrum of complex 17 in the positive mode shows a mass cluster
centred at m/z 1640.4 corresponding to C47H60Cl2O10Si2Sn6+ [M – 2COCH3 – 7Ph +
H2O + CH2Cl2 + H+]+ (See Supporting Information Figure S.161, 162). No assignments
could be made, referring most likely to one or more hydrolysis products, appear in the
119Sn, 1H, and 13C NMR spectra. Therefore, further investigation in solution were not
performed.
The triorganotin acetate 17 crystalizes in triclinic space group P–1. This crystalline mate-
rial shows low solubility in non-polar organic solvents. It is more soluble in polar organic
solvents such as acetonitrile, ethanol, ethyl acetat...
The molecular structure is presented in Figure 29, selected interatomic distances and bond
angles are listed in Table 5. Compound 17 presents a centrosymmetric head to tail dimer
via (Sn–O–C–O–Sn) bridges, composed of four eight-membered rings (Sn–O–C–O–Sn–
C–Si–C) and one central sixteen-membered ring (Sn–O–C–O–Sn–C–Si–C–Sn–O–C–O–
Sn–C–Si–C), showing a similar molecular structure as the organofluorido stannate 22.
The two neighbour acetate anions located in the eight-membered rings coordinate the
tin atom Sn(1) unsymmetrically at Sn(1)–O(5) and Sn(1)–O(7) distances of 2.212(17)
and 2.299(15) Å, respectively. As to acetate moieties adjacent to both eight- and
eighteen-membered rings, they coordinate tin atoms in almost perfect isobidentate man-
ner at Sn(2)–O(8), Sn(2)–O(10A), Sn(3)–O(6), and Sn(3)–O(9) distances of 2.276(15),
2.286(14), 2.239(14), and 2.218(15) Å, respectively. These distances are similar to
the corresponding distances in the organotin acetate HC[Sn(OAc)Ph2]3 ranging be-
tween 2.235(2) and 2.246(2) Å,[12] and those in the diorganotin carboxylate derivative
[{Me2Sn(O2CMe)}2O]2, ranging between 2.24(1) and 2.38(2) Å.[36]
Like the organofluorido stannate 22, the organotin acetate 17 contains as well a central
cavity. However, no host molecules were detected after several trials. A calculation of the
radii of a simulated guest for 17 is realized via calculation of the average of distances
between a simulated centroid of the 208 atoms and the 12 atoms situated in the cavity plan:
H(4A) 1.419 Å, H(4A’) 1.419 Å, H(2A) 2.695 Å, H(2A’) 2.695 Å, H(3B) 2.310 Å, H(3B’)
2.310 Å, O(9) 3.492 Å, O(9A) 3.492 Å, Sn(2) 4.925 Å, Sn(2A) 4.925 Å, Sn(3) 3.940 Å,
Sn(3A) 3.940 Å; with substraction of the vdW radius of each atom: H (1.06 Å), O (1.42 Å),
and Sn (2.16 Å).[5] The average of the distances with n= 12 is: 1n∑
n
i=1Xi. The radius found
equal to 1.6435 Å (Figure 33).
69
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Figure 33. POV Ray images of 17 in space fill mode (left with protons, right: without
protons): simulation of a centroid of the 208 atoms of one molecule of 17 as an imaginary
guest.
All tin atoms are pentacoordinated, exhibiting distorted trigonal-bipyramidal geometries
with geometrical goodnesses ∆Σ(θ)[22] of 87.2◦ (Sn1), 90.3◦ (Sn2), and 85.2◦ (Sn3).
The axial positions are occupied by O(5), O(7) (at Sn1), O(8), O(10A) (at Sn2), O(6),
O(9) (at Sn3). The equatorial positions are occupied by C(1), C(11), C(21) (at Sn1),
C(2), C(31), C(41) (at Sn2), C(3), C(51), C(61) (at Sn3). To conclude, the molecu-
lar structure of 17 in the solid state reveals the formation of the organotin acetate
[MeSi{CH2SnOC(O)CH3Ph2}3]2. Formally, this can be interpreted as the product of
a ring opening dimerization of a hypothetical MeSi{CH2SnOC(O)CH3Ph2}3 showing
adamantine-type structure. Consequently, we deduce that triorganotin carboxylates at-
tempt to build coordination polymers, in which the carboxylate anions coordinate the tin
centres either in unisobidentate or isobidentate manner.[36,37]
70
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Table 5. Selected interatomic distances /Å and angles /◦C in compounds 17 and 22.
17 22
Sn(1)–O(5) 2.212(17)
Sn(1)–O(7) 2.299(15)
Sn(2)–O(8) 2.276(15)
Sn(2)–O(10A) 2.286(14)
Sn(3)–O(6) 2.239(14)
Sn(3)–O(9) 2.218(15)
Sn(1)–F(1) 2.166(4)
Sn(1)–F(4) 2.172(4)
Sn(2)–F(2) 2.032(4)
Sn(2)–F(4) 2.258(4)
Sn(3)–F(1A) 2.226(4)
Sn(3)–F(3) 2.043(4)
O(5)–Sn(1)–O(7) 178.7(5)
O(5)–Sn(1)–C(1) 94.5(8)
O(8)–Sn(2)–O(10A) 177.9(6)
C(31)–Sn(2)–C(2) 124.6(8)
O(6)–Sn(3)–O(9) 176.5(6)
O(9)–Sn(3)–C(3) 95.9(8)
F(1)–Sn(1)–F(4) 178.9(14)
F(1)–Sn(1)–C(21) 90.32(16)
C(11)–Sn(1)–C(21) 120.8(18)
F(2)–Sn(2)–F(4) 177.34(18)
F(2)–Sn(2)–C(2) 94.9(3)
C(2)–Sn(2)–C(31) 114.9(3)
F(3)–Sn(3)–F(1A) 177.69(14)
F(1A)–Sn(3)–C(3) 86.7(2)
C(3)–Sn(3)–C(51) 124.2(2)
2.2.5 Complexation behaviour of 9 towards bromide anions
The ability of the nonabromido-substituted organotinderivative 9 to chelate bromide anions
is studied. Thus, a 119Sn NMR spectrum of compound 9 in CD2Cl2 at room temperature,
to which one molar equiv of tetraphenylphosphonium bromide, [PPh4]Br, had been added
shows a broad signal at δ –353 ppm, W1/2 = 780 Hz without 119/117Sn NMR satellites
indicating an exchange process that is fast on the NMR scale (See Supporting Information,
71
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Chapter 2, Figure S210). This resonance is very low-frequency shifted in comparison to the
parent compound 9 (δ –210 ppm) and proves the formation of a new organobromido stan-
nate complex. The complex [PPh4][MeSi(CH2SnBr3)3·Br], 23, (Scheme 14) was isolated
as single-crystalline material from a mixture of diethyl ether/ dichloromethane.
Scheme 14. Reaction of 9 with one molar equiv PPh4Br.
PPh4 Si
Me
Sn
Sn
Sn
Br
Br
Br
Br
Br
Br
Br Br
Br
Br
PPh4Br, 
CH2Cl2
23
Si
Me
Sn
Sn
Sn
Br
Br
Br
Br
Br
Br
Br
Br
Br
9
Compound 23 crystallizes as its dichloromethane solvate, 23·0.5CH2Cl2, in the mono-
clinic space group P–1. Figure 34 shows its molecular structure. Table 6 contains selected
interatomic distances and angles.
72
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Figure 34. General view (POV-Ray) of a molecule of 23 ·0.5CH2Cl2 showing crystallo-
graphic numbering scheme. Hydrogen atoms, the PPh4+ cation and the CH2Cl2 solvate
molecule are omitted for clarity.
The molecular structure of 23·0.5CH2Cl2 shows that Sn(2) and Sn(3)chelate the bromide
anion Br(10) unsymmetrically at Sn(2)–Br(10) and Sn(3)–Br(10) distances of 2.8756(3)
and 3.0349(9) Å, respectively, forming a six-membered ring (Si–C–Sn–Br–Sn–C). The
Sn(1) centre is [4+1]-coordinated and exhibits a distorted trigonal-bipyramidal environ-
ment, with angles varying between 103.44(3)◦ (Br2–Sn1–Br3) and 118.30(17)◦ (C1–Sn1–
Br1). The Br(7) atom approaches the Sn(1) via the face defined by Br(1), Br(3), C(1) at a
Sn(1)–Br(7) distance of 4.0690(10) Å. Sn(1)–Br distances vary between 2.4507(8) Å (Sn1–
Br3) and 2.4610(8) Å (Sn1–Br2). As for Sn(2) and Sn(3), Sn-Br distances vary between
2.5335(9) Å (Sn3–Br4) and 2.5713(8) Å (Sn2–Br7).
The Sn(2) and Sn(3) atoms are pentacoordinated, exhibiting distorted trigonal bipyramidal
environments, with geometrical goodness ∆Σ(θ)[22] equal to 72.5◦ with C(2), Br(8), and
Br(9) occupying the equatorial positions and Br(7) and Br(10) occupying the axial posi-
tions at Sn(2) and a ∆Σ(θ)[22] equal to 64.6◦ with C(3), Br(5), and Br(6) occupying the
equatorial positions and Br(4) and Br(10) occupying the axial positions at Sn(3). These dis-
73
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
tortions are explained by Br(7)–Sn(2)–Br(10) and Br(4)–Sn(3)–Br(6) angles, respectively
of 178.31(3)◦ and 177.74(3)◦, deviating from the ideal angle of 180◦.
We further investigate the behaviour of 23 in solution. A 119Sn NMR spectrum in CD2Cl2
at −80 ◦C shows an unresolved broad signal. This is very common for such compounds
given their kinetic lability even at low temperature. The 1H and 13C NMR spectra of the
same sample support the formation of the bromidostannate complex 23. The 1H NMR
spectrum shows the SiCH3 single resonance at δ 0.71 ppm, displaced to slightly lower
frequency in comparison to that of 9 (δ 0.76 ppm). As to the SiCH2Sn resonance appears
at δ 2.31 ppm, shifting to higher frequency in comparison with the methylene protons of 9
(δ 1.96 ppm). In a 13C NMR spectrum, the resonances corresponding to SiCH3 at δ 1.87
ppm are slightly lower-frequency shifted comparing to 9 (δ 2.21 ppm) and SiCH2Sn at
δ 27.56 ppm displace to higher frequencies in comparison with that of 9 at δ 11.25 ppm
(Table 7).
An ESI-MS spectrum of 23 in the positive mode shows one mass cluster centred at m/z
339.3 assigned to the cation [PPh4]+ and in the negative mode a mass cluster centred at
1242.1 corresponding to [M – PPh4+]– : [MeSi(CH2SnBr3)3·Br]– (See Supporting Infor-
mation, Chapter 2, Figures S207- S214).
We witness the formation of the 1:1 anionic adduct 23 in a bidentate manner, when the
nonabromido derivative 9 in which are three halogen substituents on each tin atoms, reacts
with one equiv molar of bromide. However, there is formation of the 1:2 anionic adduct
13, resulting from the reaction of the dihalogenido-substituted compound 4 with one equiv
molar of chloride. This difference of the complexation behaviour between 4 and 9 can
be explained, that the third tin atom in 9, not involved in the complexation, is satisfied
by interaction with three bromine atoms. This is not the case in compound 4. As it was
already mentioned before, the chelation behaviour is related always to the geometry of
each compound and its Lewis-acidity.[3]
A 119Sn NMR spectrum at ambient temperature of a solution of 9 in CD2Cl2, to which
two molar equiv of NEt4Br had been added, shows a very broad resonance at δ –424
ppm, W1/2 = 34 408 Hz, (see Supporting Information Figure S.219) very low-frequency
shifted in comparison to the parent compound 9 (δ –210 ppm). This proves the formation
of a novel organobromidostannate complex. A colourless crystalline material is isolated
from a diethyl-ether/dichloromethane solution suitable for X-ray diffraction study. Fig-
ure 35 shows the molecular structure of the complex 24 (NEt4)2[MeSi(CH2SnBr3)3·2Br],
confirming the formation of a 1:2 adduct (Scheme 15).
74
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Scheme 15. Reaction of 9 with two molar equiv NEt4Br.
24
Si
Me
Sn
Sn
Sn
Br
Br
Br
Br
Br
Br
Br
Br
Br
9
Si
Me
Sn
Sn
Sn
Br
Br
Br
Br
Br
Br
Br Br
Br
Br
Br
NEt4 2
2 NEt4Br, 
CH3CN
Figure 35. General view (POV-Ray) of a molecule of 24 showing crystallographic num-
bering scheme. Hydrogen atoms and NEt4+ cations are omitted for clarity.
75
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Complex 24 crystallizes in the orthorhombic space group Pba2, from an acetonitrile/
dichloromethane solution. Figure 35 shows its molecular structure and Table 6 contains
selected interatomic distances and angles. The Sn(1) and Sn(2) centres are intramolecularly
non-symmetrically bridged via Br(4), at Sn1–Br4 and Sn2–Br4 distances of 2.735(5) and
3.439(3) Å, respectively. There is a formation of a six membered cycle (Si–C–Sn-Br–Sn–
C) via this Sn–Br–Sn bridge. The third tin centre Sn(3) chelates the second bromide anion.
Sn(3)–Br distances vary between 2.485(2) Å (Sn3–Br11) and 2.660 Å (Sn3–Br9). All
tin atoms are pentacoordinated and exhibit distorted-trigonal bipyramidal environments
with geometrical goodness[22] ∆Σ(θ) = 83.3◦ (Sn1), 44.6◦ (Sn2), and 88.8◦ (Sn3). The
equatorial positions are occupied by C(1), Br(1), Br(3) at Sn(1), C(2), Br(6), Br(7) at Sn(2),
and C(3), Br(8), Br(11) at Sn(3). The axial positions are occupied by Br(2), Br(4) at Sn(1),
Br(4), Br(5) at Sn(2), and Br(9), Br(10) at Sn(3).
The 1:2 anionic adduct 24 exhibits an approachable complexation behaviour as the
organochlorido stannate 13. However, this latter resulted from the reaction of 4 with
only one molar equiv of chloride anion. This is due maybe to the high Lewis acidity
of the nonabromido derivative 9, and that all tin atoms are satisfied with four coordinated
bromine atoms. This has a significant connection with the complexation behaviour of
complex 14, in which the hexachlorido derivative 4 reacts with only two molar equiv of
chloride anions, though every tin atom chelate one additional third chloride anion.
76
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Table 6. Selected interatomic distances /Å and angles /◦C in compounds 23 ·0.5CH2Cl2
and 24.
23 24
Sn(1)–Br(2) 2.4610(8) 2.622(3)
Sn(1)–Br(3) 2.4507(8) 2.486(2)
Sn(1)–Br(7) 4.0690(10)
Sn(2)–Br(10) 2.8756(8)
Sn(3)–Br(10) 3.0349(9)
Sn(1)–Br(4) 2.735(5)
Sn(2)–Br(4) 3.439(3)
Sn(3)–Br(9) 2.660(2)
Sn(3)–Br(11) 2.485(2)
Br(2)–Sn(1)–Br(3) 103.44(3)
Br(1)–Sn(1)–C(1) 118.30(17)
Br(7)–Sn(2)–Br(10) 177.74(3)
Br(7)–Sn(2)–C(2) 94.96(17)
C(2)–Sn(2)–Br(9) 121.33(17)
Br(4)–Sn(3)–Br(10) 178.31(3)
C(3)–Sn(3)–Br(4) 97.77(16)
C(3)–Sn(3)–Br(5) 128.77(16)
Br(5)–Sn(3)–Br(6) 106.52(3)
Br(2)–Sn(1)–Br(4) 176.19(10)
Br(2)–Sn(1)–C(1) 95.3(5)
C(1)–Sn(1)–Br(3) 121.2(4)
Br(4)–Sn(2)–Br(5) 175.70(10)
C(2)–Sn(2)–Br(5) 103.0(5)
Br(6)–Sn(2)–Br(7) 105.83(10)
Br(9)–Sn(3)–Br(10) 175.31(8)
C(3)–Sn(3)–Br(10) 92.5(6)
C(3)–Sn(3)–Br(8) 135.0(5)
A 119Sn NMR spectrum at −80 ◦C shows an unresolved broad signal which cannot be
defined which prevents a detailed NMR spectroscopic studies in solution even at low
temperature due to fast exchange processes undergoing. As to the 1H and 13C NMR
spectra of the same sample support the formation of 24. The 1H NMR spectrum displays
a single resonance for the SiCH3 protons at δ 0.81 ppm and for the SiCH2Sn resonance at
77
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
δ 2.39 ppm. These are shifted to higher frequencies in comparison with the corresponding
resonances in 9 (δ 0.76, 1.96 ppm). The resonances referring to the CH2 protons (δ 3.15
ppm, 16H) and the CH3 protons (δ 1.21 ppm, 24H) indicate the presence of two NEt4+
cations. In a 13C NMR spectrum, the resonances corresponding to SiCH3 at δ –3.41
ppm and SiCH2Sn at δ 15.22 ppm shifting to lower frequencies in comparison with the
corresponding resonances of 9, respectively, at δ 2.21 and 18.94 ppm. As to the resonances
referring to the NEt4+ cations, the CH3 carbon signal appears at δ 7.83 ppm and the CH2
carbon signal at δ 53.19 ppm (Table 7).
An ESI-MS spectrum of 24 in the positive mode shows one mass clus-
ter centred at m/z 130.3 assigned to the cation [NEt4]+ and in the negative
mode a mass cluster centred at 1240.1 and 1534.2 corresponding, respectively, to
[M – Br– – 2NEt4+]– : [MeSi(CH2SnBr3)3·Br]– and [M – NEt4+ + 2CH3CN]– :
{[MeSi(CH2SnBr3)3·2Br]2 –}·NEt4+ + 2CH3CN (See Supporting Information, Chapter
2, Figures S216- S225).
In fact, upon the addition of a third molar equiv of [PPh4]Br in CD2Cl2, a 119Sn NMR
spectrum shows a very broad single resonance at δ –511 ppm, W1/2 = 2438 Hz (See Sup-
porting Information, Chapter 2, Figure S220). It is shifted to lower frequency comparing to
that of the nonabromido derivative 9 (δ –210 ppm), and the two organobromidostannates
complexes 23 (δ –353 ppm) and 24 (δ –424 ppm). This finding can be considered, with
caution, as prove for the formation of a new complex in solution. However, no crystalline
material was isolated from this reaction mixture. Therefore, there is no confirmation that
each tin atom is satisfied via interactions with a maximum of four bromide atoms. No
further investigation in solution is realized giving the difficulties of 119Sn NMR measure-
ments of such kinetically label compounds even at low temperatures.
Table 7. Selected NMR data measured in CD2Cl2 and CD3CN solutions of the bromide
complexes.
δ 13C(CH2) δ 1H(CH2) δ 119Sn(RT) δ 119Sn(−80 ◦C)
23 27.04 2.31 –353 –
24 15.22 (CD3CN) 2.39 (CD3CN) –424 –
2.3 Conclusion
The novel spacer-bridged tritin compounds MeSi{CH2SnXnR(3 –n)}3 (X = Cl, Br, F; n
= 1– 3) exhibits a chelation ability towards both neutral and charged Lewis bases, in a
78
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
bidentate rather than a tridentate manner. This finding come to defend the affirmation
saying that spacer-bridged tri- and tetranuclear organotin compounds attempt to chelate
Lewis bases in a bidentate manner, not as expected in a tridentate or tetradentate one.[3] In
fact, the tin atoms, not involved in the complexation process are satisfied due to additional
intramolecular interactions giving the specificity of each compound’s geometry or a luck of
Lewis-acidity. Secondly, we underline the characteristic of these tripod organtin derivatives
to build organostannate complexes having cavities in their skeletons. This refers to the
possibility of such compounds for hosting guest molecules. This theme will be more
interpreted in the coming chapters. However, in a similar context, the next chapter will
focuss on the study of the chelation ability of a novel tetranuclear organotin compound
R'Sn(CH2SnR(3 –n) Xn)3, (n = 0 - 2; X = I, Cl; R = Ph, R'= R, X) towards Lewis bases
taking as example chloride anions.
2.4 Experimental Section
• Synthesis of tris(chloromethyl)methylsilane MeSi(CH2Cl)3 (1)[24]
A 2.5 M solution of n-butyllithium in hexane (40.14 mL, 100.35 mmol,) was added drop-
wise at −70 ◦C within a period of 5 h to a magnetically stirred mixture consisting of
trichloromethylsilane (5.00 g, 33.45 mmol), and bromochloromethane (19.47 g, 150.52
mmol) in THF (200 mL). The n-butyllithium solution was added via a special horizontally
elongated side neck of the three-necked flask, which itself was immersed in the cooling
bath to ensure precooling of the n-butyllithium solution before making contact with the
reaction mixture. After completion of the addition, the mixture was stirred at −78 ◦C for
another 5 h and then, the reaction mixture was warmed to room temperature overnight.
The solvent was removed under reduced pressure. The residue thus obtained was extracted
with diethyl ether (400 mL) and washed with distilled water (3 × 100 mL) in order to
remove the remaining salts. The organic phase was dried over MgSO4 and filtrated. The
solvent of the filtrate and excess of BrCH2Cl were removed under reduced pressure. The
residue was purified by distillation (65 ◦C, 12 mbar) to give 1 as a colourless liquid (4.61 g,
24.09 mmol, 72 % yield).[24] 1H NMR (C6D6, 400.25, 298 K): δ 0.06 ppm (s, 3H, SiCH3),
2.60 ppm (s, 6 H, SiCH2Cl), 13C NMR (C6D6, 100.64, 298 K): δ –8.53 ppm (SiCH3),
25.60 ppm (SiCH2Cl). 29Si NMR (C6D6, 79.52, 298 K): δ 1.6 ppm (SiCH3).
• Synthesis of tris(triphenylstannylmethyl)methylsilane MeSi(CH2SnPh3)3 (2)
To a solution of SnPh3Cl (10 g, 25.94 mmol,) in THF (250 mL) were added metallic
sodium (1.43 g, 62.26 mmol) and a catalytic amount of naphthalene. The mixture was
stirred at room temperature for 3 days, during which its colour changed to deep black.
Further activation to accelerate the process was realized by sonification with ultrasound
79
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
(45 min). After the solution had been separated from non-reacted sodium, 1 (1.65 g, 8.62
mmol,) was added dropwise at −70 ◦C under magnetic stirring. Overnight, the reaction
mixture was warmed to room temperature and the solvent was evaporated in vacuo. The
residue obtained was extracted with 300 mL diethyl ether followed by washing with 150
mL distilled water in order to remove the sodium chloride. The organic phase was dried
over anhydrous MgSO4 and filtrated. The solvent was removed from the filtrate under
reduced pressure, giving 2 as amorphous white solid (9.59 g, 8.54 mmol, 98 % yield). Fur-
ther purification was achieved by recrystallization from hot iso-hexane to give transparent
needles with a mp of 132 ◦C.
1H NMR (CDCl3, 400.25, 298 K): δ –0.19 ppm (s, 3H, SiCH3), 0.33 ppm (s, 6H,
2J(1H – 117/119Sn) = 78 Hz, SiCH2Sn), 7.30-7.44 ppm (complex pattern, 45H, Ph). 13C{1H}
NMR (CDCl3, 150.94, 298 K): δ –1.7 ppm (3J(13C – 117/119Sn) = 20 Hz, 1J(13C – 29Si) =
48 Hz, 1J(13C – 117/119Sn) = 262/274 Hz, SiCH2Sn), 3.9 ppm (3J(13C – 117/119Sn) = 12 Hz,
1J(13C – 29Si) = 51 Hz, SiCH3), 128.4 ppm (3J(13C – 117/119Sn) = 49 Hz, Cm), 128.7 ppm
(4J(13C – 117/119Sn) = 10 Hz, Cp), 136.9 ppm (2J (13C – 117/119Sn) = 37 Hz, Co), 139.6 ppm
(1J(13C – 117/119Sn) = 460/492 Hz, Ci). 29Si NMR (CDCl3, 79.52, 298 K): δ 8.7 ppm
(2J(29Si – 117/119Sn) = 21 Hz, SiCH2Sn). 119Sn NMR (CDCl3, 149.26, 298 K): δ –89 ppm
(SnPh3). Anal. Calcd (%) for C58H54SiSn3: C 61.36, H 4.79. Found: C 61.3, H 4.8. Elec-
trospray MS: m/z (%) positive mode 119.1 (100, Sn+), 383.0097 C18H15SnO2+ (50, [M –
C40H43SiSn2 + 2H2O]).
• Synthesis of tris(diiodidophenylstannylmethyl)methylsilane
MeSi(CH2SnPhI2)3 (3)
Over a period of 10h, elemental iodine (8.39 g, 33.06 mmol, 6 equiv) was added in
small portions at 0 ◦C to a stirred solution of 2 (6.36 g, 5.60 mmol, 1 equiv). The stir-
ring was continued and the reaction mixture was warmed to room temperature overnight.
Dichloromethane and iodobenzene were removed in vacuo (10−3 mmHg) to afford 3 as a
yellow oil in 99 % yield (7.95 g, 5.54 mmol).
1H NMR (CDCl3, 400.25, 298 K): δ 0.53 ppm (s, 3H, SiCH3), 1.71 ppm (s, 6H,
2J(1H – 117/119Sn) = 84 Hz, SiCH2Sn), 7.43-7.73 ppm (complex pattern, 15H, Ph).
13C{1H} NMR (CDCl3, 150.94, 298 K): δ 3.23 ppm (3J(13C – 117/119Sn) = 20 Hz,
1J(13C – 29Si) = 40 Hz, SiCH3), 11.9 ppm (3J(13C – 117/119Sn) = 20 Hz, 1J(13C – 29Si)
= 50 Hz, 1J(13C – 117/119Sn) = 259/272 Hz, SiCH2Sn), 129.2 ppm (3J(13C – 117/119Sn) =
78 Hz, Cm), 131.1 ppm (4J(13C – 117/119Sn) = 16 Hz, Cp), 134.1 ppm (2J (13C – 117/119Sn) =
59 Hz, Co), 136.5 ppm (1J(13C – 117/119Sn) = 580/601 Hz, Ci). 29Si NMR (CDCl3, 119.26,
298 K): δ 8.8 ppm (2J(29Si – 117/119Sn) = 36 Hz, SiCH2Sn). 119Sn NMR (C6D6, 149.26,
298 K): δ –228 ppm (SnI2Ph). Anal. Calcd (%) for C22H24I6SiSn3: C 18.43, H 1.69.
Found: C 18.8, H 1.9. Electrospray MS: m/z (%) positive mode 392.1 I2SnH3O+ (30, [M –
80
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
C22H24I4SiSn2 + H+ + H2O]+), 721.0 C16H19ISiSn3+ (15, [M – C6H5I5]+), m/z (%) nega-
tive mode 127.3 I– (8, [M – C22H24I5SiSn3]– ), 381.0 I3 – (100, [M – C22H24I3SiSn3]– ),
1450.3017 (C22H25I6OSiSn3 *1.00[M + OH – ]– + C22H24I6ClSiSn3 * 0.10[M + Cl – ]– ),
1560.1988 C22H24I7OSiSn3 – ([M + I]– ).
• Synthesis of tris(dichloridophenylstannylmethyl)methylsilane
MeSi(CH2SnPhCl2)3 (4)
To a solution of 3 (1.17g, 0.813 mmol) in CH2Cl2 (150 mL) was added excess of silver
chloride (1.05g, 7.32 mmol). The resulting mixture was stirred at room temperature in the
dark for 14 days. The formed AgI and the non-reacted AgCl was removed by filtration. The
CH2Cl2 of the filtrate was evaporated in vacuo (10−3 mmHg) to afford an oily transparent
substance in 98 % yield (0.707 g, 789 µmol).
1H NMR (C6D6, 400.25, 298 K): δ 0.65 ppm (s, 3H, SiCH3), 1.18 ppm (s, 6H,
2J(1H – 117/119Sn) = 84 Hz, SiCH2Sn), 7.07-7.50 ppm (complex pattern, 15H, Ph).
13C{1H} NMR (C6D6, 100.64, 298 K): δ 3.5 ppm (3J(13C – 117/119Sn) = 22 Hz,
1J(13C – 29Si) = 40 Hz, SiCH3), 11.2 ppm (3J(13C – 117/119Sn) = 25 Hz, 1J(13C – 29Si) =
47 Hz, 1J(13C – 117/119Sn) = 361/376, SiCH2Sn), 130.1 ppm (3J(13C – 117/119Sn) = 87 Hz,
Cm), 132.1 ppm (4J(13C – 117/119Sn) = 16 Hz, Cp), 134.9 ppm (2J (13C – 117/119Sn) = 66 Hz,
Co), 139.7 ppm (1J(13C – 117/119Sn) = 742/773 Hz, Ci). 29Si NMR (C6D6, 79.52, 298 K):
δ 7.4 ppm (2J(29Si – 117/119Sn) = 49 Hz, SiCH2Sn). 119Sn NMR (C6D6, 149.26, 298 K):
δ 41 ppm (SnPhCl2). Anal. Calcd (%) for C22H24Cl6SiSn3: C 29.85, H 2.73. Found: C
29.5, H 2.9. Electrospray MS: m/z (%) positive mode 738.7 C16H21Cl4SiSn3+ (25, M –
Ph – 2Cl– + H+]+), 766.8694 C21H24Cl3SiSn3+ (100, [M – Me – 3Cl– + H+]+), 776.8050
C16H22Cl5SiSn3+.
• Synthesis of tris(iodidodiphenylstannylmethyl)methylsilane
MeSi(CH2SnPh2I)3 (5)
Over a period of 3 h, elemental iodine (0.341 g, 1.34 mmol, 2.88 equiv) was added
in small portions at 0 ◦C to a stirred solution of 2 ( 0.529 g, 465.97 µmol, 1 equiv) in
dichloromethane. The stirring was continued and the reaction mixture was warmed to
room temperature overnight. Dichloromethane and iodobenzene were removed in vacuo
(10−3 mmHg) to afford a slightly yellow oil in 95 % yield (0.502 g, 391.18 µmol). Further
purification was realized by repeatedly wash with iso-hexane.
1H NMR (CDCl3, 400.25, 298 K): δ 0.15 ppm (s, 3H, SiCH3), 0.99 ppm (s, 6H,
2J(1H – 117/119Sn) = 80 Hz, SiCH2Sn), 7.35-7.67 ppm (complex pattern, 15H, Ph). 13C{1H}
NMR (CDCl3, 150.94, 298 K): δ 3.76 ppm (3J(13C – 117/119Sn) = 15 Hz, SiCH3), 4.14
ppm (3J(13C – 117/119Sn) = 23 Hz, 1J(13C – 29Si) = 48 Hz, 1J(13C – 117/119Sn) = 253, 264 Hz,
SiCH2Sn), 128.8 ppm (3J(13C – 117/119Sn) = 60 Hz, Cm), 129.9 ppm (4J(13C – 117/119Sn) =
81
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
14 Hz, Cp), 135.8 ppm (2J (13C – 117/119Sn) = 50 Hz, Co), 137.6 ppm (1J(13C – 117/119Sn) =
520/544 Hz, Ci). 29Si NMR (CDCl3, 119.26, 298 K): δ 8.97 ppm (2J(29Si – 117/119Sn) =
28 Hz, SiCH2Sn). 119Sn NMR (CDCl3, 223.85, 298 K): δ –67 ppm (SnIPh2). Anal. Calcd
(%) for C40H33I3SiSn3: C 37.4, H 3.06. Found: C 38.3, H 3.4. Electrospray MS: m/z
(%) positive mode 919.2 C39H44NaSiSn3+ (100, [M – Me – 3I– + 4H+ + Na+]+), 969.2
C12H23I3O2SiSn3+ (100, [M – 5Ph– + 6H+ + Na+ + 2MeOH]+), m/z (%) negative mode
127.3 I– (100, [M – C40H33I2SiSn3+]– ).
• Synthesis of tris(chloridodiphenylstannylmethyl)methylsilane
MeSi(CH2SnPh2Cl)3 (6)
To a solution of 5 (4.93 g, 3.84 mmol) in CH2Cl2 (150 mL) was added excess of silver
chloride (2.48 g, 17.28 mmol). The resulting mixture was stirred at room temperature in
the dark for 14 days. The fored AgI and the non-reacted AgCl was removed by filtration.
The CH2Cl2 of the filtrate was evaporated in vacuo (10−3 mmHg) to afford amorphous
white solid (3.80 g, 3.76 mmol, 97 % yield). Further purification was achieved by recrys-
tallization from CH2Cl2/diethyl ether to give transparent needles.
1H NMR (CDCl3, 600.29, 298 K): δ 0.35 ppm (s, 3H, SiCH3), 0.96 ppm (s, 6H,
2J(1H – 117/119Sn) = 79 Hz, SiCH2Sn), 7.45-7.78 ppm (complex pattern, 30H, Ph).
13C{1H} NMR (CDCl3, 150.94, 298 K): δ 3.6 ppm (3J(13C – 117/119Sn) = 15 Hz,
1J(13C – 29Si) = 40 Hz, SiCH3), 4.13 ppm (3J(13C – 117/119Sn) = 21 Hz, 1J(13C – 29Si) =
48 Hz, 1J(13C – 117/119Sn) = 285/296, SiCH2Sn), 128.94 ppm (3J(13C – 117/119Sn) = 63 Hz,
Cm), 130.14 ppm (4J(13C – 117/119Sn) = 12 Hz, Cp), 135.51 ppm (2J (13C – 117/119Sn) =
60 Hz, Co), 139.21 ppm (1J(13C – 117/119Sn) = 564/589 Hz, Ci). 29Si NMR (CDCl3, 79.52,
298 K): δ 8.61 ppm (2J(29Si – 117/119Sn) = 30 Hz, SiCH2Sn). 119Sn NMR (C6D6, 149.26,
298 K): δ 24 ppm (SnPh2Cl). Anal. Calcd (%) for C40H39Cl3SiSn3: C 47.55, H 3.89.
Found: C 47.2, H 3.9. Electrospray MS: m/z (%) positive mode 957.2 C33H38NaSiSn3+
(100, [M – Me – Ph+H2O+H+]+), m/z (%) negative mode 1044.8610 [C40H39Cl4SiSn3]–
(100, [M + Cl – ]– ), 1136.7966 [C40H39Cl3ISiSn3]– (100, [M + I – ]– ).
• Synthesis of tris(fluoridodiphenylstannylmethyl)methylsilane
MeSi(CH2SnPh2F)3 (7)
A solution of 3 (376 mg, 0.292 mmol) in CH2Cl2 (25 mL) was mixed with excess of KF
(153mg, 2.63 mmol) in water (20 mL). The biphasic mixture was stirred at room temper-
ature for 3 days. The organic phase was then separated, dried over MgSO4, and filtered.
Removing the solvent in vacuo afforded a white solid (270 mg, 0.28 mmol, 95 % yield).
Further purification was achieved by several wash with water, methanol, acetone... to give
an amorphous white solid. Anal. Calcd (%) for C40H39F3SiSn3: C 50, H 4.09. Found: C
47.6, H 4.1 calculated for (C40H39F3SiSn3+ H2O + HF). Electrospray MS: m/z (%) nega-
82
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
tive mode 255.2263 SnH2F7 – [80, (SnF62 – + HF+ H+)]– and 978.9520 C40H39F4SiSn3 –
[40, (M + F – )]– .
• Synthesis of tris(dibromidodiphenylstannylmethyl)methylsilane
MeSi(CH2SnPhBr2)3 (8)
To a cooled solution (−55 ◦C) of 2 (479 mg, 0.421 mmol) in CH2Cl2 (30 mL) was added
dropwise a solution of bromine (403.89 mg, 2.53 mmol) in CH2Cl2 (15 mL). After the ad-
dition was completed, the mixture was stirred and warmed to room temperature overnight.
From the orange-red solution obtained, the solvent and the PhBr formed were removed in
vacuo (10−3 mmHg) to afford a light-yellow oil (480 mg, 416 mmol, 98 %).
1H NMR (CDCl3, 400.25, 298 K): δ 0.65 ppm (s, 3H, SiCH3), 1.57 ppm (s, 6H,
2J(1H – 117/119Sn) = 88 Hz, SiCH2Sn), 7.50-7.75 ppm (complex pattern, 15H, Ph). 13C{1H}
NMR (CDCl3, 100.64, 298 K): δ 3.26 ppm (3J(13C – 117/119Sn) = 22 Hz, SiCH3), 11.85
ppm (3J(13C – 117/119Sn) = 29 Hz, 1J(13C – 29Si) = 47 Hz, 1J(13C – 117/119Sn) = 318/333,
SiCH2Sn), 129.53 ppm (3J(13C – 117/119Sn) = 86 Hz, Cm), 131.57 ppm (4J(13C – 117/119Sn)
= 20 Hz, Cp), 134.28 ppm (2J (13C – 117/119Sn) = 63 Hz, Co), 138.87 ppm. 29Si NMR
(C6D6, 119.26, 298 K): δ 7.52 ppm (2J(29Si – 117/119Sn) = 44 Hz, SiCH2Sn). 119Sn NMR
(C6D6, 223.85, 298 K): δ –16 ppm (SnPhBr2). Anal. Calcd (%) for C22H24Br6SiSn3: C
22.94, H 2.1. Found: C 23.9, H 2.4 calculated for (C22H24Br6SiSn3 +CH3CN+H2O). Elec-
trospray MS: m/z (%) positive mode 721.0 C12H20Br2NSiSn3+ (100, [M – 4Br– – 2Ph +
CH3CN + H+]+), m/z (%) negative mode 79.5 (100, Br – )– , 944.7 C3H13Br6O2SiSn3 –
(30, [M – Me – 3Ph + H2O + OH – ]– ).
• Synthesis of tris(tribromidodiphenylstannylmethyl)methylsilane
MeSi(CH2SnBr3)3 (9)
To a cooled solution (−55 ◦C) of 2 (491 mg, 0.432 mmol) in CH2Cl2 (30 mL) was added
dropwise a solution of bromine (1.01 g, 3.98 mmol) in CH2Cl2 (40 mL). After the addition
was completed, the mixture was stirred and warmed to room temperature overnight. From
the red solution obtained, the solvent and the PhBr formed were removed in vacuo (10−3
mmHg) to afford an orange-brown solid (684 mg, 0.432 mmol, 99 %). Further purification
was achieved by recrystallization from CH2Cl2/diethyl ether to give orange needles.
1H NMR (CDCl3, 400.25, 298 K): δ 0.76 ppm (s, 3H, SiCH3), 1.96 ppm (s, 6H,
2J(1H – 117/119Sn) = 120/126 Hz, SiCH2Sn). 13C{1H} NMR (CDCl3, 100.64, 298 K):
δ 2.21 ppm (3J(13C – 117/119Sn) = 26 Hz, 1J(13C – 29Si) = 57 Hz, SiCH3), 18.94 ppm
(3J(13C – 117/119Sn) = 37 Hz, 1J(13C – 29Si) = 77 Hz, 1J(13C – 117/119Sn) = 414/430,
SiCH2Sn). 29Si NMR (CDCl3, 79.52, 298 K): δ 6.09 ppm (2J(29Si – 117/119Sn) = 45 Hz,
SiCH2Sn). 119Sn NMR (CDCl3, 149.26, 298 K): δ –210 ppm (SnBr3). Anal. Calcd (%) for
C4H9Br9SiSn3: C 4.14, H 0.78. Found: C 4.6, H 0.9. Electrospray MS: m/z (%) positive
83
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
mode 356.3 PhSnBr2H2+ (100, [PhSnBr2H + H+])+, 725.5 C4H11Br5NOSn2+ (50, [M –
MeSiC2H4SnBr4 + MeOH + CH3CN + H+])+, m/z (%) negative mode 358.8 SnBr3 – (100,
[M – MeC3H6SiSn2Br6])– .
• Synthesis of tris[diphenyl(trimethylsilylmethyl)stannylmethyl)methylsilane
MeSi[CH2Sn(CH2SiMe3)Ph2]3 (10)
A solution of MeSi(CH2SnPh2I)3, 5 (4.77g, 3.56 mmol, 0.9 equiv) in THF (120 mL) was
added dropwise to a solution of Me3SiCH2MgCl, prepared from Me3SiCH2Cl (1.46 g,
11.87 mmol, 3 equiv) and magnesium (0.307 g, 12.66 mmol, 3.2 equiv) in THF (40 mL),
for a period of 1 h. After the addition had been completed, the reaction mixture was heated
to reflux overnight and then cooled to room temperature. THF was distilled off under
reduced pressure; then cold water (50 mL) was added, and the mixture was extracted three
times with 100 mL diethyl ether. The combined organic phases were dried over MgSO4
and the solvents removed under reduced pressure, giving 10 as a slightly yellow oil (4.341
g, 3.73 mmol, 94 %). Further purification was achieved by several wash with iso-hexane.
1H NMR (CDCl3, 600.29, 298 K): δ –0.24 ppm (s, 3H, SiCH3), –0.15–0.12 ppm
(s, 27H, Si(CH3)3), 0.04 ppm (s, 6H, CH2SiMe3), 0.10 ppm (s, 6H, 2J(1H – 117/119Sn)
= 72/74 Hz, SiCH2Sn), 7.30-7.41 ppm (complex pattern, 30H, Ph). 13C{1H} NMR
(CDCl3, 100.46, 298 K): δ –3.33 ppm (1J(13C – 117/119Sn) = 255/267 Hz, CH2SiMe3),
-0.06 ppm (3J(13C – 117/119Sn) = 21 Hz, 1J(13C – 117/119Sn) = 248/266 Hz, SiCH2Sn),
1.53 ppm (3J(13C – 117/119Sn) = 14 Hz, 1J(13C – 29Si) = 51 Hz , Si(CH3)3), 3.85 ppm
(3J(13C – 117/119Sn) = 12 Hz, SiCH3), 128.1 ppm (Cm), 128.4 ppm (Cp), 136.7 ppm
(2J (13C – 117/119Sn) = 38 Hz, Co), 141.4 ppm (1J(13C – 117/119Sn) = 452/477 Hz, Ci). 29Si
NMR (CDCl3, 79.52, 298 K): δ 7.84 ppm (2J(29Si – 117/119Sn) = 26 Hz, SiCH3), 2.68 ppm
(1J(29Si – 13C) = 51 Hz, CH2SiMe3). 119Sn NMR (CDCl3, 223.85, 298 K): δ –49 ppm
(SnCH2SiMe3Ph2). Anal. Calcd (%) for C52H72Si4Sn3: C 53.58, H 6.23. Found: C 54.2,
H 6.2. Electrospray MS: m/z (%) positive mode 1129.3 (10, C43H69Cl2O2Si3Sn3+).
• Synthesis of tris[diiodido(trimethylsilylmethyl)stannylmethyl)methylsilane
MeSi[CH2Sn(CH2SiMe3)I2]3 (11)
Over a period of 3h, elemental iodine (0.769 g, 3.03 mmol, 6 equiv) was added in small
portions at 0 ◦C to a stirred solution of 10 ( 0.589 g, 505.31 µmol, 1 equiv). The stir-
ring was continued and the reaction mixture was warmed to room temperature overnight.
Dichloromethane and iodobenzene were removed in vacuo (10−3 mmHg) to afford a yellow
solid in 99 % yield (0.732 g, 500.25 µmol).
1H NMR (CDCl3, 400.25, 298 K): δ 0.16-0.23 ppm (s, 27H, Si(CH3)3), 0.67 ppm
(s, 3H, SiCH3), 1.45 ppm (s, 6H, 2J(1H – 117/119Sn) = 88/92 Hz, CH2SiMe3), 1.72 ppm
(s, 6H, 2J(1H – 117/119Sn) = 74 Hz, SiCH2Sn). 13C{1H} NMR (CDCl3, 150.94, 298 K):
84
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
δ 0.74-1.74 ppm (3J(13C – 117/119Sn) = 26 Hz, 1J(13C – 29Si) = 52 Hz, Si(CH3)3), 3.13
ppm (3J(13C – 117/119Sn) = 18 Hz, SiCH3), 12.60 ppm (1J(13C – 117/119Sn) = 242/254 Hz,
1J(13C – 29Si) = 49 Hz, (3J(13C – 117/119Sn) = 24 Hz, SiCH2Sn), 14.74 ppm (1J(13C – 29Si)
= 43 Hz, 1J(13C – 117/119Sn) = 251/264 Hz, CH2SiMe3). 29Si NMR (CDCl3, 79.52, 298
K): δ 3.81 ppm (2J(29Si – 117/119Sn) = 39 Hz, 1J(29Si – 13C) = 53 Hz, CH2SiMe3), 9.52
ppm (2J(29Si – 117/119Sn) = 44 Hz, SiMe). 119Sn NMR (CDCl3, 149.26, 298 K): δ –190
ppm (SnCH2SiMe3I2). Anal. Calcd (%) for C16H42I6Si4Sn3: C 13.12, H 2.89. Found: C
13.1, H 2.9. Electrospray MS: m/z (%) positive mode 824.9353 C4H12I3SiSn3+ (100, [M –
(CH2SiMe3I)3 + H+]+).
• Synthesis of tris[dichlorido(trimethylsilylmethyl)stannylmethyl)methylsilane
MeSi[CH2Sn(CH2SiMe3)Cl2]3 (12)
To a solution of 11 (1.59 g, 13.6 mmol, 1 equiv). in CH2Cl2 (150 mL) was added excess
of silver chloride (13.64 g, 95.2 mmol, 7 equiv). The resulting mixture was stirred at
room temperature in the dark for 14 days. The formed AgI and the non-reacted AgCl was
removed by filtration. The CH2Cl2 of the filtrate was evaporated in vacuo (10−3 mmHg)
to afford a white solid in 98 % yield (12.2 g, 13.328 mmol, 1 equiv).
1H NMR (CDCl3, 400.25, 298 K): δ 0.06-0.40 (s, 27H, SiMe3), 0.59 (s, 3H, SiMe),
0.97 (s, 6H, 2J(1H – 117/119Sn) = 95/100 Hz, CH2SiMe3), 1.2 (s, 6H, 2J(1H – 117/119Sn) =
75 Hz, SiCH2Sn). 13C{1H} NMR (CDCl3, 100.46, 298 K): δ 1.03 (3J(13C – 117/119Sn)
= 33 Hz, 1J(13C – 29Si) = 54 Hz, SiMe3), 1.5 (3J(13C – 117/119Sn) = 20 Hz, SiCH3), 2.98
(3J(13C – 117/119Sn) = 20 Hz, 1J(13C – 29Si) = 54 Hz, SiCH2Sn), 14.09 (3J(13C – 117/119Sn)
= 35 Hz, 1J(13C – 117/119Sn) = 328/342 Hz, CH2SiMe3). 29Si NMR (CDCl3, 79.52,
298 K): δ 7.29 (2J(29Si – 117/119Sn) = 54 Hz, SiMe), 2.7 (2J(29Si – 117/119Sn) = 41 Hz,
CH2SiMe3). 119Sn NMR (C6D6, 149.26, 298 K): δ 131 (SnCH2SiMe3Cl2). Anal. Calcd
(%) for C16H42Cl6Si4Sn3: C 20.99, H 4.62. Found: C 22.4, H 4.7 calculated for
(C16H42Cl6Si4Sn3 + CH3CN + H2O). Electrospray MS: m/z (%) positive mode 778.929
C8H29Cl5O4Si2Sn3+ (100, [M – Cl– – 2CH2SiMe3 + 4H2O + H+])+.
Complexation Studies
• Synthesis of (C11H21N2)2[MeSi(CH2SnPhCl2)3·2Cl] (13)
Imidazolium chloride (16.16 mg, 0.074 mmol) is added to a solution of 4 (66 mg, 0.074
mmol) in 15 mL CH2Cl2 and the mixture is stirred at room temperature overnight. The sol-
vent is evacuated to afford a white solid. Re-crystallization from dichloromethane/toluene
give 35 mg (42 %) of pure 13 as colourless crystals of mp 250 ◦C. 119Sn NMR (CD3CN,
149.26): at −30 ◦C δ –153. 119Sn NMR (CD2Cl2, 149.26): at −80 ◦C δ –49(1.7), –151(1.3).
Given a loss of material, no further investigations of the structure of 13 in solid state or in
solution are realized.
85
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
• Synthesis of (C11H21N2)3[MeSi(CH2SnPhCl2)3·3Cl] (14)
Imidazolium chloride (55.33 mg, 0.255 mmol) is added to a solution of 4 (113 mg,
0.127 mmol) in 20 mL CH2Cl2 and the mixture is stirred at room temperature overnight.
The solvent is evacuated to afford a white solid. Re-crystallization from acetoni-
trile/dichloromethane give 80 mg (47 %) of pure 14 as colourless crystals of mp 273 ◦C.
1H NMR (CD3CN, 600.29, 298 K): δ 0.58 (s, 3H, SiMe), 1.42 (s, 6H, 2J(1H – 117/119Sn)
= 152 Hz, SiCH2Sn), 1.65 (s, 54H, t-Bu), 7.36-8.17 ppm (complex pattern, 15H, Ph),
7.64 (d, 6H, CH), 8.63 (t, 3H, CH). 13C{1H} NMR (CD3CN, 150.49, 298 K): δ 3.67
(3J(13C – 117/119Sn) = 19 Hz, SiCH3), 27.49 (3J(13C – 117/119Sn) = 40 Hz, SiCH2Sn), 121.27
(CH, C11H21N2+), 132.91 (CH, C11H21N2+), 128.91 ppm (3J(13C – 117/119Sn) = 98 Hz,
Cm), 130.05 ppm (4J(13C – 117/119Sn) = 18 Hz, Cp), 136.51 ppm (2J (13C – 117/119Sn) =
64 Hz, Co), 150.59 ppm (1J(13C – 117/119Sn) = 985 Hz, Ci). 29Si NMR (CD3CN, 119.26,
298 K): δ 2.73 (2J(29Si – 117/119Sn) = 38 Hz, SiMe). 119Sn NMR (CDCl3, 149.26, 298 K):
δ –160, W1/2 = 255 Hz (crude mixture), 119Sn NMR (CDCl3, 149.26, 298 K): δ –175
(crystals sample) (SnCl). Anal. Calcd (%) for C55H87Cl9N6SiSn3: C 43.02, H 5.71. N
5.47 Found: C 42.7, H 5.7, N 5.6. Electrospray MS: m/z (%) positive mode 721.0 [M –
3(C11H21N2)+ – 6Cl– – Ph + H2O]+, 739.0 [M – 3(C11H21N2)+ – 5Cl– + H+]+, 1504.3
[M – Cl– – N– + H+ + H2O]+.
• Reaction of 4 with three equiv molar (C11H21N2Cl)
Imidazolium chloride (61.7 mg, 0.284 mmol) is added to a solution of 4 (84 mg, 0.094
mmol) in 20 mL CH2Cl2 and the mixture is stirred at room temperature overnight. The
solvent is evacuated to afford an oily transparent substance. 119Sn NMR (CD3CN, 149.26,
298 K): δ –178 (SnCl). No crystalline material is isolated. No further investigations are
done.
• Synthesis of (PPh4)[MeSi(CH2SnCH2SiMe3Cl2)3·NO3] (15)
Tetraphenylphosphoinium nitrate is synthesized according to literature[33] and character-
ized via IR spectroscopy (See Supporting Information S.142). To a solution of NO3PPh4
(67.55 mg, 0.168 mmol) is added solution of 4 (149 mg, 0.168 mmol) in 25 mL CH2Cl2.
The mixture is stirred at room temperature overnight. The solvent is evacuated to afford a
colourless oily substance. No crystalline material is isolated.
1H NMR (CDCl3, 400.25, 298 K): δ 0.65 (s, 3H, SiMe), 1.56 (s, 6H, 2J(1H – 117/119Sn) =
102 Hz, SiCH2Sn), 1.65 (s, 54H, t-Bu), 7.30– 8.03 ppm (complex pattern, 20H + 15H, 4 +
PPh4+). 13C{1H} NMR (CDCl3, 100.64, 298 K): δ 2.22 (3J(13C – 117/119Sn) = 31 Hz,
SiCH3), 18.33 (3J(13C – 117/119Sn) = 21 Hz, SiCH2Sn), (130.7, Cm (PPh4+)), (117.7, Cp
(PPh4+)), (134.2, Co (PPh4+)), and (135.7, Ci (PPh4+)), 128.5 ppm (3J(13C – 117/119Sn) =
86
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
89 Hz, Cm), 130.08 ppm (4J(13C – 117/119Sn) = 20 Hz, Cp), 135.1 ppm (2J (13C – 117/119Sn)
= 68 Hz, Co), 143.7ppm. 31P NMR (CDCl3, 162.02, 298 K): δ 23.18 PPh4+.
119Sn NMR (CDCl3, 400.25, 298 K): δ –84 (crude mixture). Anal. Calcd (%)
for C46H44Cl6NO3PSiSn3: C 42.94, H 3.45, N 1.09. Found (%) of C 43.0, H
3.75, N 0.6. Electrospray MS: m/z (%) negative mode 62.7 [NO3]– , 1125.3
{[(MeSi(CH2SnCl2Ph)3 ·NO3]– + HPPh2 + H2O}– , 1152.3 [(C22H25Cl3SiSn3)3+ +
3OH– + NO3 – + 2H2O + 3CH3CN + MeOH]– .
• Synthesis of [MeSi(CH2SnCl2Ph)3 ·3HMPA] (16)
A solution of HMPA (59.51 mg, 0.332 mmol) is added to a solution of 4 (98.00 mg, 0.110
mmol) in 5 mL CH2Cl2 and the mixture is stirred at room temperature overnight. The
solvent is removed in vacuo, and the oily residue is dissolved in 25 mL of a mixture
acetonitrile/dichloromethane. Slow evaporation of the solvents affords 126 mg (80 %) of
pure 16 as colourless crystals of mp 205 ◦C.
1H NMR (CDCl3, 600.29, 298 K): δ 0.58 (s, 3H, SiMe), 1.53 (s, 6H, 2J(1H – 117/119Sn)
= 117 Hz, SiCH2Sn), 2.55 (d, 54H, 3J(1H – 31P) = 137 Hz, N(CH3)2), 7.38– 8.03 ppm
(complex pattern, 15H, Ph). 13C {1H} NMR (CDCl3, 150.49, 298 K): δ 4 (SiCH3),
18.33 (1J(13C – 117/119Sn) = 519 Hz, SiCH2Sn), 36.7 (N(CH3)2), 128.4 (3J(13C – 117/119Sn)
= 95 Hz, Cm), 129.8 (Cp), 135.06 (2J (13C – 117/119Sn) = 69 Hz, Co), 145.3 ppm
(1J(13C – 117/119Sn) = 912/964 Hz, Ci). 31P {1H} NMR (CD2Cl2, 162.02, 193 K): δ
23.5 (2J(31P – 117/119Sn) = 181 Hz, POSn), 23.8 (8 %, no assignment), 24.7 (8 %, no
assignment), 25.2 (8 %, no assignment). 119Sn NMR (CDCl3, 400, 298 K): δ –187
(crude mixture, W1/2 = 809 Hz), 119Sn NMR (CD2Cl2, 149.26, 193 K): δ –216 (crys-
tals sample) (m, 74 %, SnCl), -253 (5 %, no assignment), -252 (5 %, no assignment), -190
(5 %, no assignment). IR (KBr) νP=O = 1121.9 cm−1. Electrospray MS: m/z (%) posi-
tive mode 180.1 [POH(NMe2)3]+, 740.8 [C12H42Cl3N6O4P2Sn2]+, negative mode, 810.7
[C18H23Cl4NO2SiSn3]– . Anal. Calcd (%) for C40H78Cl6N9O3P3SiSn3: C 33.76, H 5.53,
N 8.86. Found: C 33.6, H 5.5, N 8.8.
• Synthesis of {MeSi[CH2Sn(OCOCH3)Ph2]3}2 (17)
Three molar equivalents of silver acetate (60.42 mg, 0.361 mmol) were added to a solution
of 5 (155 mg, 0.120 mmol) in 40 mL CH2Cl2 and the mixture is stirred at room temperature
in the dark for seven days. The AgI formed is removed by filtration. Re-crystallization
from dichloromethane/diethyl-ether gives 39 mg (30 %) of pure 17 as colourless crystals
of mp 210 ◦C.
29Si NMR (CDCl3, 119.26, 298 K): δ –21.9 (2J(29Si – 117/119Sn) = 36 Hz, SiMe). 119Sn
NMR (CDCl3, 400, 298 K): (crude mixture) δ –218 (10 %), –204 (W1/2 = 682 Hz, 46 %),
–171 (7 %), –167 (6 %), –91/–90 (19 %), and –44 (10 %). 119Sn NMR (CDCl3, 400.25,
87
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
193 K): (crystals sample) δ –91 (2Sn1’), –90 (2 Sn1), –40 (4J(119Sn2 – 117/119Sn1/Sn1’)
= 220 Hz, 2Sn2). IR (KBr) νC=O = 1539 cm−1, νC−O = 1428, 1018 cm−1. Electrospray
MS: m/z (%) positive mode 1640.4 C47H60Cl2O10Si2Sn6+ [M – 2COCH3 – 7Ph + H2O +
CH2Cl2 + H+]+. Anal. Calcd (%) for C92H96O12N2Si2Sn6 + 3H2O + C6H14: C 51.1, H
5.08. Found: C 51.1, H 5.2.
• Reaction of 6 with four equiv molar HMPA: formation of
{[MeSi(CH2SnCl2Ph2)2(CH2SnPh2) ·2HMPA][MeSi(CH2SnCl2Ph2)(CH2Sn
Ph2Cl)(CH2SnPh2) ·2HMPA]} (18) and [MeSi(CH2SnClPh2)3 ·3HMPA]+HMPA
(19)
A solution of HMPA (82.76 mg, 0.461 mmol) is added to a solution of 4 (117 mg, 0.115
mmol) in 10 mL CH2Cl2 and the mixture is stirred at room temperature overnight. The
solvent is removed in vacuo, and the oily residue is dissolved in 25 mL of a mixture
acetonitrile/dichloromethane. Slow evaporation of the solvents affords 100 mg (56 %)
of a crystalline material of 18 and 19. Due to difficulties in the separation of these two
compounds, there is no intensive study in solution of each compound separately.
1H NMR (CDCl3, 600.29, 298 K): (crude mixture) δ 0.23 (s, 3H, SiMe), δ 0.86 (s,
6H, 2J(1H – 117/119Sn) = 92 Hz, SiCH2Sn), 2.46 (d, 72H, 2J(1H – 1H) = 9 Hz, 3J(1H – 31P)
= 135 Hz, N(CH3)2), 7.31-8.03 (complex pattern, 30H, Ph). 13C {1H} NMR (CDCl3,
150.49, 298 K): (crude mixture) δ 3.44 (SiCH3), 9.05 (SiCH2Sn), 36.2 (N(CH3)2), 127.9
(3J(13C – 117/119Sn) = 66 Hz, Cm), 128.8 (Cp), 135.7 (2J (13C – 117/119Sn) = 52 Hz, Co),
142.9 ppm (Ci). 31P {1H} NMR (CDCl3, 243, 298 K): δ 24 (crude mixture). 31P {1H}
NMR (CD2Cl2, 162.02, 193 K (-80 ◦C)): (crystals sample) δ 23.28 (s, 48 %), 23.62 (broad
signal, 39 %), 22.7 (5 %), 24.1 (3 %), 24.3 (4 %). 119Sn NMR (CDCl3, 223.58, 298 K): δ
–81 (crude mixture) (broad signal, W1/2 = 1675 Hz), 119Sn NMR (CD2Cl2, 149.26, 193
K (−80 ◦C)): (crystals sample) δ –104 (s, 1.2), -133 (s, 3.5), -170 (broad signal, W1/2 =
920 Hz, 1.4), -185 (broad signal,W1/2 = 950 Hz, 1.2), -197 (t, 2J(31P – 117/119Sn) = 313 Hz,
1.9). To distinguish between these two compounds in solution, we need more probably a
much lower temperature 119Sn and 31P NMR measurements. Within the time frame of this
PhD, further investigation in solution could not be performed.
Electrospray MS: m/z (%) negative mode 1291.1 [(MeSi(CH2SnCl3Ph2)3·HMPA +
PClOH– – (NMe2)3]– , 1046.1 [(MeSi(CH2SnCl3Ph2)(CH2SnClPh2)(CH2SnO2Ph2)]2 – .
Anal. Calcd (%) for C52H77Cl3N6O2P3SiSn3 (18): C 45.56, H 5.66, N 6.13. Found: C
46.1, H 5.6, N 5.8. Anal. Calcd (%) for C64H111Cl3N12O4P4SiSn3 (19): C 44.48, H
6.48, N 9.73, found C 44.4, H 6.4, N 9.2.
• Reaction of 6 with one equiv molar PPh4Cl: (PPh4)[MeSi(CH2SnPh2Cl)3 ·Cl]
(20)
88
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
Tetraphenylphosphonium chloride (33.02 mg, 0.088 mmol) is added to a solution of 6
(89 mg, 0.088 mmol) in 20 mL CH2Cl2 and the mixture is stirred at room temperature
overnight. The solvent is evacuated to afford (PPh4)[MeSi(CH2SnPh2Cl)3·Cl], 20 (119
mg, 97 %) as an amorphous white substance. No crystalline material is isolated.
1H NMR (CDCl3, 400.25, 298 K): δ 0.3 (s, 3H, SiMe), 0.92 (s, 6H, 2J(1H – 117/119Sn) =
98 Hz, SiCH2Sn), 7.24- 8.01 (complex pattern, 20H (PPh4) + 30H (20), Ph). 13C{1H}
NMR (CDCl3, 100.64, 298 K): δ 2.96 (3J(13C – 117/119Sn) = 21 Hz, SiCH3), 12.05
(SiCH2Sn), 127.9 (3J(13C – 117/119Sn) = 62 Hz, Cm), 128.6 (4J(13C – 117/119Sn) = 12 Hz,
Cp), 136.56 (2J (13C – 117/119Sn) = 49 Hz, Co), 143.7 ppm (Ci), 117.2 (Cp, PPh4), 130.6
(Cm, PPh4), 134.1 (Co, PPh4), 135.7 (Ci, PPh4). 29Si NMR (CDCl3, 119.26, 298 K): δ
5.72 (2J(29Si – 117/119Sn) = 36 Hz, SiMe). 119Sn NMR (CDCl3, 149.26, 298 K): δ –77
(crude mixture, W1/2 = 980 Hz), 119Sn NMR (CD2Cl2, 223.85, 193 K (-80 ◦C)): δ –87
(1Sn), –52 (2Sn). Electrospray MS: m/z (%) negative mode 1026.7902 [M – PPh4+ –
Cl– + OH – ]– . Anal. Calcd (%) for C63H59Cl4PSiSn3: C 55.50, H 4.29. Found: C 54.5, H
4.3.
• Reaction of 6 with two equiv molar PPh4Cl:
(PPh4)2[MeSi(CH2SnPh2Cl)3 ·2Cl] (21)
Tetraphenylphosphonium chloride (54.17 mg, 0.144 mmol) is added to a solution of 6
(73 mg, 0.072 mmol) in 25 mL CH2Cl2 and the mixture is stirred at room temperature
overnight. The solvent is evacuated to afford (PPh4)2[MeSi(CH2SnPh2Cl)3·2Cl], 21 (124
mg, 98 %) as an amorphous white substance. No crystalline material is isolated.
1H NMR (CD2Cl2, 400.25, 298 K): δ 0.31 (s, 3H, SiMe), 0.97 (s, 6H, 2J(1H – 117/119Sn)
= 100 Hz, SiCH2Sn), 7.24– 8.15 (complex pattern, 40H (PPh4) + 30H (21), Ph). 13C{1H}
NMR (CD2Cl2, 100.64, 298 K): δ 3.62 (3J(13C – 117/119Sn) = 25 Hz, SiCH3), 14.21
(3J(13C – 117/119Sn) = 23 Hz, SiCH2Sn), 128.2 (3J(13C – 117/119Sn) = 64 Hz, Cm), 128.8
(4J(13C – 117/119Sn) = 15 Hz, Cp), 137.1 (2J (13C – 117/119Sn) = 48 Hz, Co), 145.9 ppm
(Ci), 117.9 (Cp, PPh4), 131.1 (Cm, PPh4), 134.8 (Co, PPh4), 136.2 (Ci, PPh4). 29Si NMR
(CD2Cl2, 79.52, 298 K): δ 5.53 (2J(29Si – 117/119Sn) = 37 Hz, SiMe). 119Sn NMR (CD2Cl2,
149.26, 298 K): δ –109 (crude mixture, W1/2 = 957 Hz, 88 %), –89 (1.2 %), –134 (4.4 %),
–252 (6.8 %). No further investigation in solution is made given the ignorance of the aspect
of 21 in solid state. Electrospray MS: m/z (%) positive mode 339.2 [PPh4]+, 919.2 [M –
2PPh4+ – 2Cl– – CH3 + H+]+. Anal. Calcd (%) for C88H79Cl5P2SiSn3: C 60.05, H 4.52.
Found: 59.6, H 4.6.
• Synthesis of (NEt4)2[MeSi(CH2SnFPh2)32 ·2F] (22)
Tetraethylammonium fluoride (10.99 mg, 0.059 mmol) is added to a solution of 7 (57
mg, 0.059 mmol) in 10 mL CH3CN and the mixture is stirred at room temperature
89
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
overnight. The solvent is evacuated to afford a white solid. Re-crystallization from ace-
tonitrile/dichloromethane give 60 mg (89 %) of pure 22 as colourless crystals of mp 240
◦C.
19F NMR (CD3CN, 564.84, 298 K): (crude mixture) δ –81 (20 %), –129 (12 %), –142
(22 %), –159 (15 %), –161 (25 %). 119Sn NMR (CD3CN, 223.85, 298 K): δ –188 (crude
mixture, W1/2 = 957 Hz). Given the low solubility of the crystals of 22, at −40 ◦C and
−80 ◦C, there are no reliable 19F or 119Sn NMR spectra. Electrospray MS: m/z (%) negative
mode 979.2 [MeSi(CH2SnFPh2)3·F]– . Anal. Calcd (%) for C96H118F8N2Si2Sn6 + H2O:
C 51.5, H 5.4, N 1.25. Found: C 51.3, H 5.4, N 1.2.
• Reaction of 7 with two equiv molar of (NEt4.2H2O)
Tetraethylammonium fluoride (26.22 mg, 0.141 mmol) is added to a solution of 7 (68
mg, 0.070 mmol) in 20 mL CH2Cl2 and the mixture is stirred at room temperature
overnight. The solvent is evacuated to afford a white solid. Re-crystallization from acetoni-
trile/dichloromethane give 70 mg (92 %), the same crystalline material as 22 (mp 240 ◦C)
19F NMR (CD3CN, 564.84, 298 K): (crude mixture) δ –162 (1J(19F1 – 117/119Sn1) =
1939/2018 Hz, 1F1), –158 (1J(19F4 – 117/119Sn1) = 2010 Hz, 1F4), -142 (1J(19F2 – 117/119Sn)
= 1930 Hz, 1F2), -129 (1F3). 119Sn NMR (CD3CN, 223.85, 298 K): (crude mixture)
δ –220 (1Sn1), –213 (1Sn1), –205 (1Sn2) . Given the low solubility of the crystals of
22 at −40 ◦C and −80 ◦C, there are no reliable 19F or 119Sn NMR spectra. Electrospray
MS: m/z (%) negative mode 979.2 {20, [MeSi(CH2SnFPh2)3 ·F]– }. Anal. Calcd (%) for
C96H118F8N2Si2Sn6 + H2O + 2CH3CN: C 51.7, H 5.5, N 2.4. Found: C 51.6, H 5.8, 2.3.
• Reaction of 7 with three equiv molar of (NEt4.2H2O)
Tetraethylammonium fluoride (35.86 mg, 0.193 mmol) is added to a solution of 7 (62
mg, 0.064 mmol) in 25 mL CH2Cl2 and the mixture is stirred at room temperature
overnight. The solvent is evacuated to afford a white solid. Re-crystallization from acetoni-
trile/dichloromethane give 60 mg (87 %), the same crystalline material as 22 (mp 240 ◦C).
19F NMR (CD3CN, 564.84, 298 K): (crude mixture) major specie (94 %): δ –
158 (nJ (19F – 117/119Sn) = 2013 Hz, 2F), –142 (nJ (19F – 117/119Sn) = 1899 Hz
, 2F), –129 (nJ (19F – 117/119Sn) = 1153 Hz, 1F), minor specie (6 %): δ –162
(nJ (19F – 117/119Sn) = 1942/2029 Hz, 3F), -154 (nJ (19F – 117/119Sn) = 1506/1585 Hz,
1F), -140 (nJ (19F – 117/119Sn) = 2334/2373 Hz, 2F), -127 (nJ (19F – 117/119Sn) =
2182/2214 Hz,nJ(19F – 19F) = 116 Hz, 2F) . 29Si NMR (CD3CN, 119.26, 298 K):
δ 6.17 (2J(29Si – 117/119Sn) = 35 Hz, SiMe). 119Sn NMR (CD3CN, 223.85, 298 K):
(crude mixture) δ –270 (t, W1/2 = 1983 Hz, 1Sn), –211 (dd, 2Sn) . A crystals sample
shows the same behaviour in solution via 19F and 119Sn NMR spectra. Electrospray
90
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
MS: m/z (%) negative mode 978.2 [MeSi(CH2SnFPh2)3 ·F]– . Anal. Calcd (%) for
C96H118F8N2Si2Sn6 + 2H2O + 2CH3CN: C 51.3, H 5.5, N 2.4. Found: C 51.1, H 6.9, N
2.2.
• Synthesis of (PPh4)[MeSi(CH2SnBr3)3 ·Br] (23)
Tetraphenylphosphonium bromide (32.16 mg, 0.077 mmol) is added to a solution of
9 (89 mg, 0.077 mmol) in 15 mL CH2Cl2 and the mixture is stirred at room tempera-
ture overnight. The solvent is evacuated to afford a white solid. Re-crystallization from
dichloromethane/diethyl-ether give 100 mg (82 %) of pure 23 as colourless crystals of mp
250 ◦C.
1H NMR (CD2Cl2, 400.25, 298 K): δ 0.71 (s, 3H, SiMe, 2.31 (s, 6H, 2J(1H – 117/119Sn)
= 129/135 Hz, SiCH2Sn), 7.58–7.95 ppm (20H, PPh4+). 13C{1H} NMR (CD2Cl2, 100.64,
298 K): δ 1.87 (SiCH3), 27.56 (3J(13C – 117/119Sn) = 38 Hz, SiCH2Sn), 118.0 (Cp, PPh4),
131.2 (Cm, PPh4), 134.9 (Co, PPh4), 136.3 (Ci, PPh4). 29Si NMR (CD2Cl2, 119.26, 298 K):
δ 4.22 (2J(29Si – 117/119Sn) = 43 Hz, SiMe). 119Sn NMR (CD2Cl2, 223.85, 298 K): (crude
mixture) δ –353 (W1/2 = 780 Hz). Electrospray MS: m/z (%) negative mode 1242.1 [M –
PPh4+]– : [MeSi(CH2SnBr3)3 ·Br]– , m/z (%) positive mode 339.3 [PPh4]+. Anal. Calcd
(%) for C28H31Br10PSiSn3 + CH3CN: C 22.2, H 2.11 Found: of C 22.1, H 2.2.
• Synthesis of (NEt4)2[MeSi(CH2SnBr3)3 ·2Br] (24)
Tetraethylammonium bromide (41.29 mg, 0.196 mmol) is added to a solution of 9 (114
mg, 0.098 mmol) in 20 mL acetonitrile and the mixture is stirred at room temperature
overnight. The solvent is evacuated to afford a white solid. Re-crystallization from ace-
tonitrile/dichloromethane give 150.6 mg (97 %) of pure 24 as colourless crystals of mp
283 ◦C.
1H NMR (CD3CN, 400.25, 298 K): δ 0.81 (s, 3H, SiMe), 1.21 (t, CH3, 24H, 2NEt4+),
2.39 (s, 6H, 2J(1H – 117/119Sn) = 141 Hz, SiCH2Sn), 3.15 (q, CH2, 16H, 2NEt4+). 13C{1H}
NMR (CD3CN, 150.94, 298 K): δ –3.41 (SiCH3), 7.83 (CH3, NEt4+), 15.22 (SiCH2Sn),
53.19 (CH2, NEt4+). 29Si NMR (CD2Cl2, 119.26, 298 K): δ 5.16 (2J(29Si – 117/119Sn)
= 50 Hz, SiMe). 119Sn NMR (CD2Cl2, 223.85, 298 K): (crude mixture) δ –424 (W1/2
= 34 408 Hz). Anal. Calcd (%) for C20H49Br11N2SiSn3: C 15.2, H 3.12, N 1.77.
Found: C 15.2, H 3.4, N 1.9. Electrospray MS: m/z (%) negative mode 1240.1
[M – Br– – 2NEt4+]– : [MeSi(CH2SnBr3)3 ·Br]– , 1534.2 [M – NEt4+ + 2CH3CN]– :
{[MeSi(CH2SnBr3)3 ·2Br]2 – } ·NEt4+ + 2CH3CN, m/z (%) positive mode 130.3 [NEt4]+.
• Reaction of 9 with three equiv molar (PPh4Br)
Tetraphenylphosphonium bromide (74.79 mg, 0.178 mmol) is added to a solution of 9
(69 mg, 0.059 mmol) in 15 mL CH2Cl2 and the mixture is stirred at room temperature
91
2. Synthesis of MeSi(CH2SnR(3 – n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3),
its Characterization, and its Complexation Behaviour toward Lewis-Bases
overnight. The solvent is evacuated to afford a yellow oily substance. 119Sn NMR (CD2Cl2,
223.85, 298 K): (crude mixture) δ –511 (W1/2 = 2438 Hz, SnBr). No crystalline material
is isolated. No further investigations are done given the high kinetic lability of such com-
pounds even at low temperature.
• Reaction of 12 with one equiv molar of (C11H21N2Cl)
Imidazolium chloride (10.18 mg, 0.046 mmol) is added to a solution of 12 (43 mg, 0.046
mmol) in 15 mL CH3CN and the mixture is stirred at room temperature overnight. The
solvent is evacuated to afford an oily transparent substance. 119Sn NMR (CD3CN, 149.26,
298 K): δ –11, W1/2 = 528 Hz, (SnCl). No crystalline material is isolated. No further
investigations are done given the luck of solubility.
• Synthesis of (C11H21N2)2[MeSi(CH2SnCH2SiMe3Cl2)3·2Cl] (25)
Imidazolium chloride (22.25 mg, 0.102 mmol) is added to a solution of 12 (47 mg,
0.051 mmol) in 15 mL CH3CN and the mixture is stirred at room temperature overnight.
The solvent is evacuated to afford a white solid. Re-crystallization from acetoni-
trile/dichloromethane give 50 mg (72 %) of pure 25 as colourless crystals of mp 281 ◦C.
1H NMR (CD3CN, 400.25, 298 K): δ 0.08-0.14 (s, 27H, SiMe3), 0.47 (s, 3H, SiMe), 0.92
(s, 6H, 2J(1H – 117/119Sn) = 110 Hz, CH2SiMe3), 1.28 (s, 6H, SiCH2Sn), 1.60 (s, 36H, t-
Bu), 7.56 (d, 4H, CH), 8.44 (t, 2H, CH). 29Si NMR (CD3CN, 119.26, 298 K): δ 1.82
(CH2SiMe3), 3.92 (2J(29Si – 117/119Sn) = 56 Hz, SiMe). 119Sn NMR (CD3CN, 400.25): at
25 ◦C, δ –48, at −40 ◦C -122, -76 (SnCl). Anal. Calcd (%) for C40H93Cl8N4Si4Sn3: C
34.76, H 6.78, N 4.05 Found: C 34.6, H 6.5, N 3.6. Electrospray MS: m/z (%) negative
mode1127.4 [M – (C11H21N2)+ – 2Cl– – 3H+]– , m/z (%) positive mode 771.1 [M –
2(C11H21N2)+ – 7Cl– – CH2SiMe3 + 2H2O + CH3CN]+.
• Reaction of 12 with three equiv molar (C11H21N2Cl)
Imidazolium chloride (62.5 mg, 0.288 mmol) is added to a solution of 12 (88 mg, 0.096
mmol) in 20 mL CH3CN and the mixture is stirred at room temperature overnight.
The solvent is evacuated to afford a white solid. Re-crystallization from acetoni-
trile/dichloromethane give 100 mg (77 %) of the same crystalline material as 25 (mp
282 ◦C). 119Sn NMR (CD3CN, 149.26, 298 K): crude mixture δ –77 (SnCl).
92
3. The Spacer-Bridged Tetrastannanes
R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R =
Ph, R'= R, X), Syntheses, Structures and Complexa-
tion Studies
3.1 Introduction
The synthesis and complexation behaviour of the spacer bridged tetratin compounds
R’Sn(CH2SnR(3 –n)Xn)3, (n = 0– 2; X = I, Cl; R = Ph, R’ = R, X), having a similar structure
as the previous tripod silicon bridged organotin MeSi(CH2SnR(3 –n) Xn)3, (n = 0– 3; X =
I, F, Cl, Br; R = Ph, CH2SiMe3) is under investigation. We want to define the chelation
characteristics of these novel backbones and compare its complexation ability with the
previous mentioned compounds. Scheme 16 shows the syntheses of the compounds 1– 5.
The numbering of compounds in this chaper is independent from the previous chapter.
Scheme 16. Syntheses of the tris(organostannylmethyl)stannane derivatives
R’Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R = Ph, R’ = R, X).
Sn
I
Sn
Sn
Sn
I
Ph
Ph
Ph
Ph
I
Ph
Ph
I
    4 I2,
CH2Cl2
− 4 PhI
Sn
Cl
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
7.5 HCl,
Diethyl ether
− 7 PhCl
4 AgCl,
CH2Cl2
− 4 AgI
Ph
Sn
Ph
Ph
Br Sn
Ph
Cl
Cl
Cl
+3 Sn
Ph
Sn
Sn
Sn
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
− 3 MgClBr
3.5 Mg,
THF, 75°C
Sn
Cl
Sn
Sn
Sn
Cl
Ph
Ph
Ph
Ph
Cl
Ph
Ph
Cl
1 2 3
4 5
93
3. The Spacer-Bridged Tetrastannanes R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R =
Ph, R'= R, X), Syntheses, Structures and Complexation Studies
3.2 Syntheses and characterization of
R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R =
Ph, R'= R, X)
The reaction of one molar equiv of SnPhCl3 in THF with three molar equiv of the
Grignard reagent Ph3SnCH2MgBr, 1,[38] under reflux overnight at 75 ◦C gives the
tris(triphenylstannylmethyl)phenylstannane PhSn(CH2SnPh3)3, 2, as a white solid ma-
terial in a very good yield.
Single crystals of compound 2 suitable for X-ray diffraction analysis are obtained by
slow evaporation from a CH2Cl2/iso-hexane at room temperature. It crystallizes in the
triclinic space group P−1. Figure 36 shows the molecular structure and selected inter-
atomic distances and bond angles are listed in Table 8. The Sn(1), Sn(2), Sn(3) and Sn(4)
are four-coordinated and show distorted tetrahedral geometries with angles varying be-
tween 102.4(3)◦ (C81–Sn4–C91) and 115.5(3)◦ (C3–Sn4–C81’). The Sn–C distances
vary from 1.984(9) Å (Sn4–C91’) and 2.330(6) Å (Sn4–C91). It is worth mentioning that
the tripod geometry characteristic of 2 is comparable to that of silicon bridged organ-
otin compound MeSi(CH2SnPh3)3. In fact, the Sn(1)–C(1)–Sn(2), Sn(1)–C(2)–Sn(3), and
Sn(1)–C(3)–Sn(4) angles of 116.9(2)◦, 121.2(3)◦, and 118.1(3)◦, respectively, presenting
the three "arms" of the tripod are similar. The environment at the "head" tin atom Sn(1) is
distorted tetrahedral with almost equal angles varying between 107.14(19)◦ (C3–Sn1–C4)
and 112.6(2)◦ (C1–Sn1–C3).
94
3. The Spacer-Bridged Tetrastannanes R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R =
Ph, R'= R, X), Syntheses, Structures and Complexation Studies
Figure 36. General view (POV-Ray) of a molecule of 2 showing the crystallographic
numbering scheme. There are disorders of the phenyl rings C(31) to C(36) and C(31’) to
C(36’) with a ratio of 51:49, C(81) to C(86) and C(81’) to C(86’) with a ratio of 50:50,
and C(91) to C(96) and C(91’) to C(96’) with a ratio of 55:45, respectively.
A 119Sn NMR spectrum (Figure 37) of a solution of compound 2 in CDCl3 shows
two singlet resonances with 3: 1 ratio, respectively at δ –78 ppm (4J(119Sn – 117Sn)
= 44 Hz, 2J(119Sn – 117/119Sn) = 245/257 Hz, 1J(119Sn – 13Ci) = 504 Hz), corresponding
to the three equivalent (terSn) atoms; Sn(2), Sn(3), and Sn(4) (Figure 33), and at δ
–34 ppm, corresponding to the head tin atom Sn(1) (gemSn). This latter shift reso-
nance is comparable to those reported for the alkyl-substituted organotin compounds
Me3Sn(C6H5) (δ 32.3 ppm) and Me3Sn(t-Bu) (δ 32.3 ppm).[27] As to the lower-frequency
shifted resonance is very close to the corresponding resonances in (Ph3Sn)2CH2 (δ –
79 ppm),[26] (Ph3SnCH2)2SnPh2 (terSn δ –79 ppm),[25] and the structurally alike com-
pounds (Ph3Sn)3CH (δ –78 ppm)[12] and the novel silicon-bridged organotin compound
MeSi(CH2SnPh3)3 at -89 ppm.
95
3. The Spacer-Bridged Tetrastannanes R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R =
Ph, R'= R, X), Syntheses, Structures and Complexation Studies
Figure 37. 119Sn NMR spectrum (149.26 MHz, CDCl3) of compound 2.
A 1H NMR spectrum of a solution of 2 in C6D6 shows a singlet resonance corresponding
to the SnCH2 protons at δ 0.43 ppm (2J(1H – 117/119Sn) = 61 Hz) , this single resonance
is close to that reported of the corresponding (SiCH2Sn) protons in MeSi(CH2SnPh3)3
at δ 0.33 ppm (2J(1H – 117/119Sn) = 78 Hz), with a smaller coupling constant. A complex
pattern appears at δ 6.97- 7.63 ppm (50H) which belongs to the phenyl protons. In a 13C
NMR spectrum of 2 in CDCl3, the singlet resonance referring to the (SiCH2Sn) carbon is
shown at δ 1.35 ppm (1J(13C – 117/119Sn) = 275 Hz). This value is higher-frequency shifted
comparing to that of MeSi(CH2SnPh3)3 at δ –1.7 ppm.
In the aromatic part, the chemical shift corresponding to the carbon atoms Cm is shown
at δ 128.9 ppm (3J(13Cm – 117/119Sn1) = 61 Hz, 5J(13Cm – 117/119Sn2) = 18 Hz), with Sn1
is the "head" Sn atom and Sn2 corresponds to the three other tin atoms. The singlet
resonances of Cp, Co, and Ci appear respectively at δ 130.21 ppm (4J(13Cp – 117/119Sn) =
14 Hz), δ 135.9 ppm (2J(13Co – 117/119Sn) = 50 Hz), and 137.0 ppm, the coupling constant
1J(13Ci – 117/119Sn) are not detected. All these data evidence that the tin atoms in compound
2 are four-coordinated with distorted tetrahedral geometries, as observed in the solid state.
An ESI MS spectrum in the positive mode shows mass clusters centred at m/z 923.1
C44H40Sn3+ (60, [M – (CH2SnPh3]+) and 1310.5 (10, [M + 12 H2O + H2O]
+), respectively
(See Supporting Information, Chapter 3 Figures S1- S7).
The treatment of compound 2 with seven molar equiv of a solution of HCL in diethyl ether
produces tris(dichloridophenylstannylmethyl)chloridostannane ClSn(CH2SnPhCl2)3, 3, in
96
3. The Spacer-Bridged Tetrastannanes R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R =
Ph, R'= R, X), Syntheses, Structures and Complexation Studies
70 % yield (Scheme 5). Compound 3 is a yellowish oil, showing good solubility in common
organic solvents such as CH2Cl2, CHCl3, and CH3CN.
A 119Sn NMR spectrum (Figure 38) of the organotin dichloride-substituted derivative 3
in C6D6 exhibits two singlet resonances, with a ratio of 3:1, respectively, at δ 26 ppm
(terSn) and δ 54 ppm (gemSn). These resonance shifts are close to that reported in the
dichloride-substituted derivative in the previous chapter MeSi(CH2SnPhCl2)3 at δ 41 ppm,
also are near to the corresponding resonance in (Ph2Cl2Sn)CH2 (δ 32 ppm).[12] There are
additional unresolved resonance signals at δ 25 ppm (25 %) and -29 ppm (9 %) indicating
the presence of by-products (See Supporting Information, Chapter 3, Figure S9). Attempts
at purifying compound 3 by re-crystallization failed. A further purification is not possible,
given the instability of such compounds toward column chromatography. Therefore, this
mixture is used in the next reactions without further purification.
Figure 38. 119Sn NMR spectrum (111.92 MHz, CDCl3) of compound 3.
A 1H NMR spectrum of compound 3 displays a singlet resonance assigned to the CH2
protons at 2.11 ppm (2J(1H – 117/119Sn) = 72 Hz) which is higher-frequency shifted as
compared to that reported in MeSi(CH2SnPhCl2)3 at δ 1.50 ppm (2J(1H – 117/119Sn) =
88 Hz) and in the cyclo-Cl2Sn(CH2SiMe2CH2)2SnCl2 at 1.02 ppm (2J(1H – 117/119Sn) =
49/52 Hz).[9] As to the complex pattern of the phenyl groups appears at δ 7.42–7.86 ppm
(See Supporting Information, Chapter 3, Figure S8).
The reaction of compound 2 with four molar equiv of elemental iodine at 0 ◦C
in CH2Cl2 gives the iodine-substituted tris(iodidophenylstannylmethyl)iodidostannane
ISn(CH2SnPh2I)3, 4, in quantitative yield as a slightly yellow oil. The corresponding organ-
otin chloride ClSn(CH2SnPh2Cl)3, 5 is obtained as a colourless oily substance through the
reaction of 4 with four molar equiv of AgCl in CH2Cl2. Compounds 4 and 5 show good
solubility in common organic solvents such as CH2Cl2, CHCl3, and CH3CN. (Scheme 16)
97
3. The Spacer-Bridged Tetrastannanes R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R =
Ph, R'= R, X), Syntheses, Structures and Complexation Studies
Single crystals of compound 4 suitable for X-ray diffraction analysis are obtained by slow
evaporation from its CH2Cl2/iso-hexane solution at room temperature. It crystallizes in
the triclinic space group P−1. Figure 39 shows the molecular structure and selected inter-
atomic distances and angles are listed in Table 8. The molecular structure of 4 preserves
as well the tripod geometry, characteristic of the novel backbones. The Sn(2), Sn(3) and
Sn(4) centres are four-coordinated and show distorted tetrahedral geometries with angles
varying between 102.55(12)◦ (C41–Sn3–I3) and 115.27(17)◦ (C51–Sn3–C2). However,
Sn(1) exhibits a [4+1] coordination via an intramolecular ISn interaction at a Sn(1)–I(2)
distance of 3.9496(4) Å that is shorter than the sum of vdW radii of tin (2.17 Å) and iodine
(1.98 Å).[31] The environment at Sn(1) is a distorted trigonal bipyramid with a geometrical
goodness[22] equal to ∆Σ(θ)= 31.1◦. The equatorial positions are occupied by C(1), C(2),
and C(3) and the axial positions are occupied by I(1) and I(2). This distortion is explained
by I(1)–Sn(1)–C(1), I(1)–Sn(1)–C(2), and I(1)–Sn(1)–C(3) angles, respectively equal to
105.55(11)◦, 102.0(25)◦, and 104.11(13)◦ deviating from the ideal angle of 90◦. The Sn–I
distances are nearly equal varying between 2.7046(4) Å (Sn4–I4) and 2.7229(4) Å (Sn1-
I1).
A 119Sn NMR spectrum of the iodido-substituted derivative 4 (Figure 40) displays two
singlet resonances, with a ratio of 3:1, respectively, at δ –66 ppm (terSn) (4J(119Sn – 117Sn)
= 54 Hz, 2J(119Sn – 117/119Sn) = 319 Hz, 1J(119Sn – 13Ci) = 553 Hz), and δ 42 ppm (gemSn)
(2J(119Sn – 117/119Sn) = 319 Hz). The resonance shift corresponding to the three terSn is
close to that reported for the structurally alike iodine-derivative MeSi(CH2SnIPh2)3 (δ
–67 ppm), as well as very similar to those reported for (IPh2Sn)2CH2 (δ –68 ppm)[26]
(IPh2Sn2CH2)2SiMe2 (δ –65 ppm),[28] (Ph2ISn)3CH (δ –70 ppm).[12]
A 1H NMR spectrum of a solution of 4 in C6D6 shows a singlet resonance corresponding
to the SnCH2 protons at δ 1.52 ppm (2J(1H – 117/119Sn) = 61 Hz) , this single resonance
is slightly higher frequency-shifted as compared to that reported for the corresponding
(SiCH2Sn) protons in MeSi(CH2SnIPh2)3 at δ 0.99 ppm (2J(1H – 117/119Sn) = 80 Hz) but
with a smaller coupling constant. Also this shift resonance is close to those correspond-
ing in (IPh2Sn2CH2)2SiMe2 (δ 1.03 ppm) and (IPh2Sn)2CH2 (δ 1.87 ppm). A complex
pattern is shown for the phenyl protons at δ 7.39-7.68 ppm (30H).
98
3. The Spacer-Bridged Tetrastannanes R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R =
Ph, R'= R, X), Syntheses, Structures and Complexation Studies
Figure 39. General view (POV-Ray) of a molecule of 4 showing the crystallographic
numbering scheme.
99
3. The Spacer-Bridged Tetrastannanes R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R =
Ph, R'= R, X), Syntheses, Structures and Complexation Studies
Figure 40. 119Sn NMR spectrum (111.92 MHz, CDCl3) of compound 4.
In a 13C NMR spectrum of 4 in CDCl3, the singlet resonance referring to the (SiCH2Sn)
carbon atom is shown at δ 1.29 ppm [(1J(13C – 117/119Sn) = 264/277 Hz]. This value is
lower-frequency shifted comparing to the corresponding reported for MeSi(CH2SnIPh2)3
at 4.14 ppm (1J(13C – 117/119Sn) = 253/264 Hz) and for (IPh2Sn2CH2)2SiMe2 (δ 3.5 ppm)
(1J(13C – 117/119Sn) = 253/267 Hz). In the aromatic part, the chemical shifts corresponding
to the carbon atoms Cm is shown at δ 128.9 ppm (3J(13Cm – 117/119Sn1) = 60 Hz. The sin-
glet resonances of Cp, Co, and Ci appear respectively at δ 130.2 ppm (4J(13Cp – 117/119Sn)
= 12 Hz), δ 135.9 ppm (2J(13Co – 117/119Sn) = 52Hz), and 137.0 ppm (1J(13Ci – 117/119Sn1)
= 543/566 Hz, 4J(13Ci – 117/119Sn2) = 10 Hz), with Sn1 being gemSn and Sn2 being terSn.
All these data prove that the tin atoms in compound 4 are four-coordinated with distorted
tetrahedral geometries, as observed in the solid state. An ESI MS spectrum in the positive
mode shows mass clusters centred at m/z 1169.0 C21H31I3O2Sn4+ (100, [M – I– – 3Ph– +
3H2O + 4H+]+) and 1250.9 C27H37I3O2Sn4+ (50, [M – Ph– – I– + 2H2O + 3H+]+),
respectively (See Supporting Information, Chapter 3, Figure S10- S15).
A 119Sn NMR spectrum of the chlorido-substituted derivative
tris(dichloridophenylstannylmethyl)chloridostannane ClSn(CH2SnClPh2)3, 5, in CDCl3
exhibits two singlet resonances, with an integral ratio of 3:1, respectively, at δ 17 ppm
(terSn) and δ 151 ppm (gemSn). The chemical shift corresponding to the terSn is close to
that reported for the dichloride-substituted derivative MeSi(CH2SnClPh2)3 at δ 24 ppm
100
3. The Spacer-Bridged Tetrastannanes R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R =
Ph, R'= R, X), Syntheses, Structures and Complexation Studies
as well to those corresponding to (ClPh2Sn)2CH2 (δ 20 ppm),[26] (Ph2ClSnCH2)2SnClPh
(terSn δ 20 ppm), (Ph2ClSnCH2SnClPh2)2CH2 (terSn δ 17 ppm). There are three
additional unresolved resonance signals having 3 % total integral at δ –90, 38, 174 ppm.
Most likely, they are referring to hydrolysis products. No further purification is realized,
given the instability of such compounds toward column chromatography. Also, attempts
for recrystallization of 5 failed. Therefore, this mixture is used without further purification
for the subsequent reactions discussed below.
A 1H NMR spectrum of compound 5 shows a singlet resonance assigned to the CH2 pro-
tons at 1.3 ppm (2J(1H – 117/119Sn) = 72 Hz) which is higher-frequency shifted in regards to
that reported in MeSi(CH2SnClPh2)3 at δ 0.96 ppm (2J(1H – 117/119Sn) = 79 Hz) and those
corresponding in (ClMe2Sn2CH2)2SiMe2 (δ 0.18 ppm), (ClPh2Sn2CH2)2SiMe2 (δ 0.79
ppm) (2J(1H – 117/119Sn) = 77/80 Hz).[28] However, this shift is lower-frequency shifted,
in comparison with that in compound (ClPh2Sn)2CH2 (δ 1.54 ppm).[26] As to the com-
plex pattern of the phenyl protons appear as complex pattern at δ 7.44-7.75 ppm with an
integration of 30H (See Supporting Information, Chapter 3, Figures S.17, S18).
101
3. The Spacer-Bridged Tetrastannanes R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R =
Ph, R'= R, X), Syntheses, Structures and Complexation Studies
Table 8. Selected interatomic distances /Å and angles /◦C in compounds 2 and 4.
2 4
Sn(2)–Br(10) 2.8756(8)
Sn(3)–Br(10) 3.0349(9)
Sn(1)–Br(4) 2.735(5)
Sn(2)–Br(4) 3.439(3)
Sn(3)–Br(9) 2.660(2)
Sn(3)–Br(11) 2.485(2)
Br(2)–Sn(1)–Br(3) 103.44(3)
Br(1)–Sn(1)–C(1) 118.30(17)
Br(7)–Sn(2)–Br(10) 177.74(3)
Br(7)–Sn(2)–C(2) 94.96(17)
C(2)–Sn(2)–Br(9) 121.33(17)
Br(4)–Sn(3)–Br(10) 178.31(3)
C(3)–Sn(3)–Br(4) 97.77(16)
C(3)–Sn(3)–Br(5) 128.77(16)
Br(5)–Sn(3)–Br(6) 106.52(3)
Br(2)–Sn(1)–Br(4) 176.19(10)
Br(2)–Sn(1)–C(1) 95.3(5)
C(1)–Sn(1)–Br(3) 121.2(4)
Br(4)–Sn(2)–Br(5) 175.70(10)
C(2)–Sn(2)–Br(5) 103.0(5)
Br(6)–Sn(2)–Br(7) 105.83(10)
Br(9)–Sn(3)–Br(10) 175.31(8)
C(3)–Sn(3)–Br(10) 92.5(6)
C(3)–Sn(3)–Br(8) 135.0(5)
3.3 Attempts for the complexation of chloride anions via
ClSn(CH2SnPhCl2)3, 3
A 119Sn NMR spectrum (CDCl3) at ambient temperature of a solution of 3 in
dichloromethane to which one molar equiv of [PPh4]Cl had been added shows four
resonance signals at δ –117 ppm (integral 24 %), -75 ppm (15 %), -32 ppm (36 %), to
which no assignments are made, in addition to the signal resonances corresponding to
the starting material at δ –28 and -54 ppm with an integration of 23 % (Figure 41).
102
3. The Spacer-Bridged Tetrastannanes R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R =
Ph, R'= R, X), Syntheses, Structures and Complexation Studies
From this reaction mixture, by addition of some iso-hexane, the organostannate com-
plexes (PPh4)[CH2(SnCl2Ph)2 ·Cl], 6, and (PPh4)2[Cl2Sn(CH2SnCl2Ph)2 ·2Cl], 7, were
isolated as crystalline materials suitable for X-ray diffraction analysis. Apparently, under
the given experimental conditions, compound 3 underwent a sort of fragmentation into
smaller molecules (Scheme 17). Figures 42 and 43 show the molecular structures of these
new complexes 6 and 7. No further investigations in solution are made given the difficulties
to characterize separately the two produced species. However, An ESI-MS mass spectrum
of complexes 6 in the negative mode shows one mass cluster centered at m/z 582.8 as-
signed to [CH2(SnCl2Ph)2 ·Cl]– , [100, M – (PPh4)+]– and in the positive mode one mass
cluster centred at m/z 339.1, corresponding to [(PPh4)+]+ (See Supporting Information,
Chapter 3, Figures S20- S23).
72 64 56 48 40 32 24 16 8 0 -8 -16 -24 -32 -40 -48 -56 -64 -72 -80 -88 -96 -104 -112 -120 -128
Chemical Shift (ppm)
24.8015.7536.1510.4012.90
54
.
35
-
28
.
59
-
32
.
10
-
32
.
81
-
74
.
72
-
75
.
44
-
76
.
19
-
11
7.
78
Figure 41. 119Sn NMR spectrum of crude mixture of the reaction of formation of 6 and 7
at ambient temperature (149.26 MHz, CDCl3).
Scheme 17. Products of the complexation attempt of the dichloride-substituted compound
3.
Sn
Cl
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
3
PPh4Cl, 
CH2Cl2 PPh4
6
Sn Sn
Ph
Cl
Cl
Ph
Cl Cl Cl
+ SnSn Sn
Ph
Cl
Cl
Cl
Cl
Ph
Cl
ClCl
Cl
2PPh4
7
103
3. The Spacer-Bridged Tetrastannanes R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R =
Ph, R'= R, X), Syntheses, Structures and Complexation Studies
The organochlorido stannate 6 crystallizes in the triclinic space group P−1. Figure
42 shows its molecular structure and the figure caption contains selected interatomic
distances and angles. The intermolecular binding mode of 6 shows, interestingly, a
tetranuclear dimer presenting a ladder-like structure via three Sn2Cl2 moieties. This
dimer is formed via unsymmetrical bridges (Sn1–Cl1A–Sn1A) and (Sn2–Cl1A–Sn1),
in which Sn(1)–Cl(1A), Sn(1A)–Cl(1A), and Sn(2)–Cl(1A) are, respectively, distant of
3.126, 2.5450(10), and 3.763 Å. All three distances are shorter than the sum of the van
der Waals radii[31] of tin (2.17 Å) and Cl (1.75 Å), and render all Sn atoms hexacoordi-
nated exhibitng a distorted octahedral all-trans SnC2Cl4 environments with angles, respec-
tively, at Sn(1) and Sn(2) of (C7–Sn1–C11) 155.46(15)◦, (Cl1A–Sn1–Cl2) 175.685(35)◦,
(Cl1–Sn1–Cl5) 173.32(3)◦, (C1–Sn2–Cl7) 144.16(15)◦, (Cl3–Sn2–Cl5) 175.74(4)◦, and
(Cl1A–Sn2–Cl4) 160.165(36)◦. These values are comparable to the corresponding angles
in (PPh4)2[HC(SnCl2Ph)3 ·2Cl].[12]
There is a chelation of Cl(5) by Sn(1) and Sn(2), via an unsymmetrical intramolecular Sn–
Cl–Sn bridge, with Sn(1)–Cl(5) and Sn(2)–Cl(5) distances of 2.6441(10) and 2.7750(10) Å,
respectively. Therefore, there is formation of a centrosymmetric doubly intramolecularly
and intermolecularly chlorido-bridged organostannate anion.
Figure 42. General view (POV-Ray) of a molecule of 6 showing crystallographic
numbering scheme and the intermolecular interaction. Hydrogen atoms and the PPh4+
cations are omitted. Selected interatomic distances (Å): Sn(1)–Cl(1A) 3.126, Sn(1A)–
Cl(1A) 2.5450(10), Sn(2)–Cl(1A) 3.763, Sn(1)–Cl(5) 2.6441(10), Sn(2)–Cl(5) 2.7750(10).
Selected interatomic angles (◦): C(7)–Sn(1)–C(11) 155.46(15), Cl(1A)–Sn(1)–Cl(2)
175.685(35), Cl(1)–Sn(1)–Cl(5) 173.32(3), C(1)–Sn(2)–Cl(7) 144.16(15), Cl(3)–Sn(2)–
Cl(5) 175.74(4), Cl(1A)–Sn(2)–Cl(4) 160.165(36).
104
3. The Spacer-Bridged Tetrastannanes R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R =
Ph, R'= R, X), Syntheses, Structures and Complexation Studies
Complex 7 crystallizes in the triclinic space group P−1. Figure 43 shows its molecular
structure and the figure caption contains selected interatomic distances and angles. The
molecular structure of 7 shows an overall perfect symmetry with intramolecular symmetri-
cal chloride interactions by Sn(2), in which the Sn(2)–Cl(3) (2.564(11) Å) and Sn(2)–Cl(4)
(2.5609(12) Å) distances are almost equal. The Sn(1)–Cl(1) and Sn(1)–Cl(2) distances of
2.3968(13) and 2.4119(12) Å, respectively, are almost equal.
Figure 43. General view (POV-Ray) of a molecule of 7 showing the crystallographic
numbering scheme. Hydrogen atoms and the PPh4+ cations are omitted. Selected in-
teratomic distances (Å): Sn(1)–Cl(1) 2.3968(13), Sn(1)–Cl(2) 2.4119(12), Sn(1)–Cl(3A)
3.109, Sn(2)–Cl(3) 2.564(11), Sn(2)–Cl(4) 2.5609(12). Selected interatomic angles (◦):
Cl(2)–Sn(1)–Cl(1) 97.98(5), Cl(1)–Sn(1)–C(7) 102.26(14), C(1)–Sn(1)–C(7) 152.03(17),
C(7)–Sn(1)–Cl(2) 97.41(13), C(7)–Sn(2)–C(7A) 180.00(18), Cl(3)–Sn(2)–Cl(3A) 180.0,
Cl(4)–Sn(2)–Cl(4A) 180.0.
The Sn(2) center is hexacoordinated by four chlorine (Cl3, Cl3A, Cl4, Cl4A) and two
carbon atoms (C7, C7A) and shows a octahedral all-trans SnC2Cl4 environment with
C(7)–Sn(2)–C(7A), Cl(3)–Sn(2)–Cl(3A), and Cl(4)–Sn(2)–Cl(4A) angles of 180.0◦.
Sn(1) and Sn(1A) display distorted tetrahedral environments, with angles varying between
97.98(5)◦ (Cl2–Sn1–Cl1) and 102.26(14)◦ (Cl1–Sn1–C7). This distortion from the theo-
retic geometry is due to the Cl(3) and Cl(3A) atoms intramolecularly and symmetrically
approaching Sn(1) and Sn(1A) at distance of 3.109 Å. These bond distances are shorter
105
3. The Spacer-Bridged Tetrastannanes R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R =
Ph, R'= R, X), Syntheses, Structures and Complexation Studies
than the sum of the van der Waals radii[31] of tin (2.17 Å) and Cl (1.75 Å), and render the
corresponding atoms [4+1]-coordinated. The geometrical goodness ∆Σ(θ)[22] at Sn(1) and
Sn(1A) is equal to 49.3◦, with C(1), Cl(2), and C(7) occupying the equatorial positions
and Cl(1) and Cl(3A) occupying the axial positions.
A 119Sn NMR spectrum (CDCl3) at ambient temperature of compound 3 to which had been
added four molar equiv of PPh4Cl, displays as well four resonances at δ –250 ppm (16 %),
-179 ppm (23 %), -141 ppm (40 %), and -59 ppm (19 %), to which no assignment is made
(See Supporting Information, Chapter 3, Figure S26). Further investigation in solution
could not be done given the difficulties to characterize complex 8 separately in presence
of other fragmentation products. Complex (PPh4)2[CH2(SnCl2Ph)2 ·2Cl], 8, (Scheme 18)
was isolated as single crystalline material suitable for X-ray diffraction studies, from a
solution of diethyl-ether/dichloromethane. Figure 44 shows the molecular structure of com-
plex 8 and the figure caption contains selected interatomic distances and angles. However,
given the lack of material no further investigations of 8 in solution were performed.
Scheme 18. Complex 8 as a product of the complexation attempt of the dichloride-
substituted compound 3.
The organochloridostannate complex 8 crystallizes, as its water solvate 8 ·0.5H2O, in
the monoclinic space group P21/n with two independent molecules in the unit cell. The
geometric parameters of both molecules resemble each other and only the structure of the
molecule containing Sn(1)- Sn(2) is discussed in detail. Figure 44 shows its molecular
structure and the figure caption contains selected interatomic distances and angles. It
consists of a centrosymmetric doubly intramolecular chloride bridges, in which each tin is
substituted with four chlorine atoms, via chelation of Cl(5) and Cl(6) by Sn(1) and Sn(2),
with bond distances of, respectively 2.9897(12) Å (Sn1–Cl5), 2.7940(11) Å (Sn1–Cl6),
2.8286(11) Å (Sn2–Cl5), and 2.7255(11) Å (Sn2–Cl6).
106
3. The Spacer-Bridged Tetrastannanes R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R =
Ph, R'= R, X), Syntheses, Structures and Complexation Studies
Sn(1) and Sn(2) centers are hexa-coordinated, exhibiting distorted octahedral all-trans
SnC2Cl4 environments with C(1)–Sn(1)–C(11), C(1)–Sn(2)–C(21), Cl(1)–Sn(1)–Cl(6),
Cl(2)–Sn(1)–Cl(5), Cl(4)–Sn(2)–Cl(6), and Cl(3)–Sn(2)–Cl(5), angles of 158.44(13)◦,
163.26(13)◦, 171.83(5)◦, 169.483(42)◦, 176.118(39)◦, 168.94(4)◦, respectively. The Sn–Cl
distances involving the non-bridging Cl atoms vary between 2.4129(39) Å (Sn1–Cl2) and
2.4874(12) Å (Sn2–Cl4). There is an intermolecular interaction between a half molecule
of water and one anion of 8 at Cl(10)· · ·H(1)O(1L) and Cl(11)· · ·H(2)O(1L) distant, re-
spectively, of 2.680 and 2.791 Å.
Figure 44. General view (POV-Ray) of a molecule of 8 ·0.5H2O showing crystallographic
numbering scheme. Hydrogen atoms and the PPh4+ cations are omitted. Selected in-
teratomic distances (Å): Sn(1)–Cl(2) 2.4129(39), Sn(1)–Cl(5) 2.9897(12), Sn(1)–Cl(6)
2.7940(11), Sn(2)–Cl(4) 2.4874(12), Sn(2)–Cl(5) 2.8286(11), Sn(2)–Cl(6) 2.7255(11),
Cl(10)–H(1)O(1L) 2.680, Cl(11)–H(2)O(1L) 2.791. Selected interatomic angles (◦): C(1)–
Sn(1)–C(11) 158.44(13), Cl(1)–Sn(1)–Cl(6) 171.83(5), Cl(2)–Sn(1)–Cl(5) 169.483(42),
C(1)–Sn(2)–C(21) 163.26(13), Cl(4)–Sn(2)–Cl(6) 176.118(39), and Cl(3)–Sn(2)–Cl(5)
168.94(4).
A 119Sn NMR spectrum of a solution of compound 3 in CDCl3 to which had been
added one molar equiv of pyridinium chloride shows five resonances at δ –95 ppm
(7.5 %), -28 ppm (29.4 %), -5 ppm (37 %), 46 ppm (6 %), and 56 ppm (20 %) to which
no assignment is made (See Supporting Information, Chapter 3, Figure S29). From
this reaction mixture, after addition of some diethyl ether, the organostannate complex
(C5H6N)2[CH2(SnCl2Ph)2 ·2Cl], 9, (Figure 45) was obtained as a colourless crystalline
material suitable for X-Ray diffraction analysis. Apparently, chloride anion caused Sn–
C bond cleavage and phenyl group migration under the given experimental conditions
(Scheme 19). However, we succeeded to have a 119Sn NMR spectrum of 9 in CDCl3,
107
3. The Spacer-Bridged Tetrastannanes R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R =
Ph, R'= R, X), Syntheses, Structures and Complexation Studies
showing a broad resonance signal at δ –30 ppm, W1/2 = 200 Hz. An ESI-MS mass spec-
trum of complex 9 in the positive mode shows one mass cluster centered at m/z 841.1
assigned to C25H33Cl6N3OSn2+, [60, M + CH3CN + H2O + H+]+. (See Supporting Infor-
mation, Chapter 3, Figures S30, S31)
Scheme 19. Reaction of compound 3 with one molar equiv pyridinium chloride giving
organochloridostannate complex 9 as the only isolated material.
Sn
Cl
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
3
1 C5H6NCl, 
CH2Cl2
9
Sn Sn
Ph
Cl
Cl
Ph
Cl
Cl Cl
2C5H6N
Cl
The organochloridostannate complex 9 crystallizes in the monoclinic space group P21/n.
Figure 37 shows its molecular structure and the figure caption contains selected inter-
atomic distances and angles. The structure of 9 resembles that of 8 ·0.5H2O with the
difference that the two pyridinium cations are involved in hydrogen bridges with the chlo-
rine atoms of the stannate anion at H(21)–Cl(4), H(21)–Cl(6), and H(31)–Cl(6) distances
of 2.782, 2.440, and 2.437 Å, respectively. The Sn(1)–Cl(5), Sn(2)–Cl(5), Sn(1)–Cl(6),
and Sn(2)–Cl(6) distances are 2.9106(13), 2.6835(12), 3.3223(14), and 2.7304(11) Å, re-
spectively. Sn(1) and Sn(2) centers are hexa-coordinated, exhibiting distorted octahedral
all-trans SnC2Cl4 environments with C(1)–Sn(1)–C(7), C(7)–Sn(2)–C(11), Cl(1)–Sn(1)–
Cl(6), Cl(2)–Sn(1)–Cl(5), Cl(4)–Sn(2)–Cl(5), and Cl(3)–Sn(2)–Cl(6), angles of 148.1(2),
170.12(16), 160.31(4), 171.03(4), 171.394(39), and 173.88(4)◦.
108
3. The Spacer-Bridged Tetrastannanes R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R =
Ph, R'= R, X), Syntheses, Structures and Complexation Studies
Figure 45. General view (POV-Ray) of a molecule of 9 showing crystallographic num-
bering scheme and NH· · ·Cl intramolecular interactions with the pyridinium cations. Se-
lected interatomic distances (Å): Sn(1)–Cl(5) 2.9106(13), Sn(2)–Cl(5) 2.6835(12), Sn(1)–
Cl(6) 3.3223(14), Sn(2)–Cl(6) 2.7304(11), N(21)H(21)–Cl(4) 2.782, N(21)H(21)–Cl(6)
2.440, and N(31)H(31)–Cl(6) 2.437. Selected interatomic angles (◦): C(1)–Sn(1)–C(7)
148.1(2), Cl(1)–Sn(1)–Cl(6) 160.31(4), Cl(2)–Sn(1)–Cl(5) 171.03(4), C(7)–Sn(2)–C(11)
170.12(16), Cl(4)–Sn(2)–Cl(5) 171.394(39), and Cl(3)–Sn(2)–Cl(6) 173.88(4).
3.4 Conclusion
Despite the similarity between MeSi(CH2SnR(3 –n) Xn)3, (n = 0– 3; X = I, F, Cl, Br; R =
Ph, CH2SiMe3) and R’Sn(CH2SnR(3 –n)Xn)3, (n = 0– 2; X = I, Cl; R = Ph, R’ = R, X), the
latter compounds show unexpected reactivity towards chloride anions. The chloride anions
induce Sn–C bond cleavage and phenyl group migration. Di- and trinuclear organochlori-
dostannate complexes were isolated, but no tetranuclear such complexes. Further studies
are needed to get deeper inside into this type of reactivity. Within the time frame of this
PhD, further studies could not be performed.
109
3. The Spacer-Bridged Tetrastannanes R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R =
Ph, R'= R, X), Syntheses, Structures and Complexation Studies
3.5 Experimental section
• Synthesis of PhSn(CH2SnPh3)3 (2)
A solution of SnPhCl3 (1.04 g, 3.44 mmol, 0.9 equiv) in THF (50 mL) was added dropwise
to a solution of Ph3SnCH2MgBr (1),[38] prepared from Ph3SnCH2Br (5.09 g, 11.46 mmol,
3 equiv) and magnesium (0.324 g, 13.37 mmol, 3.5 equiv) in THF (40 mL), for a period
of 1h. After the addition had been completed, the reaction mixture was heated to reflux
overnight and then cooled to room temperature. THF was distilled off under reduced
pressure; then cold water (50 mL) was added, and the mixture was extracted three times
with 100 mL diethyl ether. The combined organic phases were dried over MgSO4 and
the solvents removed under reduced pressure, giving 2 as a white solid (4.8 g, 3.72 mmol,
97 %). Further purification was achieved by recrystallization from CH2Cl2/ iso-hexane to
give transparent needles with a mp of 152 ◦C.
1H NMR (C6D6, 400.25, 298 K): δ 0.43 ppm (s, 6H, 2J(1H – 117/119Sn) =
61 Hz, Sn1CH2Sn2), 6.97- 7.63 ppm (complex pattern, 50H, Ph). 13C{1H} NMR
(CDCl3, 100.64, 298 K): δ 1.35 ppm (1J(13C – 117/119Sn) = 275 Hz, CH2Sn), 128.9
ppm (3J(13Cm – 117/119Sn1) = 61 Hz, 5J(13Cm – 117/119Sn2) = 18 Hz, Cm), 130.2 ppm
(4J(13Cp – 117/119Sn) = 14 Hz, Cp), 135.9 ppm (2J(13Co – 117/119Sn) = 50 Hz, Co), 137.0
ppm (Ci). 119Sn NMR (CDCl3, 149.26, 298 K): δ –73 ppm (3Sn, 4J(119Sn – 117Sn) =
44 Hz, 2J(119Sn – 117/119Sn) = 245/257 Hz, 1J(119Sn – 13Ci) = 504 Hz, Sn2), -34 ppm (1Sn,
2J(119Sn – 117/119Sn) = 245/257 Hz, Sn1). Anal. Calcd (%) for C63H56Sn4: C 58.75, H 4.38.
Found: C 58.4, H 4.4. Electrospray MS: m/z (%) positive mode 923.1 C44H40Sn3+ (60,
[M – (CH2SnPh3]+), 1310.5 (10, [M + 12 H2O + H2O]
+).
• Synthesis of ClSn(CH2SnPhCl2)3 (3)
To a solution of 2 (0.831 g, 0.645 mmol, 1 equiv) in CH2Cl2 (40 mL) was added excess of
HCl solution in diethyl ether (2 M) (0.176 g, 4.84 mmol, 7.5 equiv). The resulting mixture
was stirred at 0 ◦C overnight. Solvents were evaporated in vacuo (10−3 mmHg) to afford
a yellowish oily substance in 60 % yield (0.385 g, 386 µmol). No purification by column
chromatography could be realized given the instability of such compounds. No crystalline
material was isolated.
1H NMR (CDCl3, 400.25, 298 K): δ 2.11 ppm (s, 6H, 2J(1H – 117/119Sn) = 72 Hz,
Sn1CH2Sn2), 7.42- 7.86 ppm (complex pattern, 15H, Ph). 119Sn NMR (CDCl3, 111.92,
298 K): δ 26 ppm (3Sn, Sn2), 54 ppm (1Sn, Sn1).
• Synthesis of ISn(CH2SnPh2I)3 (4)
110
3. The Spacer-Bridged Tetrastannanes R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R =
Ph, R'= R, X), Syntheses, Structures and Complexation Studies
Over a period of 5h, elemental iodine (3.67 g, 14.47 mmol, 3.9 equiv) was added in small
portions at 0 ◦C to a stirred solution of 2 ( 4.78 g, 3.71 mmol, 1 equiv) in dichloromethane.
The stirring was continued and the reaction mixture was warmed to room temperature
overnight. Dichloromethane and iodobenzene were removed in vacuo (10−3 mmHg) to
afford a slightly yellow oil in 95 % yield (5.24 g, 3.52 mmol). Further purification was
realized by recrystallization from dichloromethane/ iso-hexane to give slightly yellow
needles with a mp of 175 ◦C.
1H NMR (CDCl3, 300.13, 298 K): δ 1.52 ppm (s, 6H, 2J(1H – 117/119Sn) = 61 Hz,
Sn1CH2Sn2), 7.39- 7.68 ppm (complex pattern, 30H, Ph). 13C{1H} NMR (CDCl3,
75.47, 298 K): δ 1.29 ppm (1J(13C – 117/119Sn) = 264/277 Hz, CH2Sn), 128.9 ppm
(3J(13Cm – 117/119Sn1) = 60 Hz, Cm), 130.2 ppm (4J(13Cp – 117/119Sn) = 12 Hz, Cp), 135.9
ppm (2J(13Co – 117/119Sn) = 52 Hz, Co), 137.0 ppm (1J(13Ci – 117/119Sn1) = 543/566 Hz,
4J(13Ci – 117/119Sn2) = 10 Hz, Ci). 119Sn NMR (CDCl3, 149.26, 298 K): δ –66 ppm (3Sn,
4J(119Sn – 117Sn) = 54 Hz, 2J(119Sn – 117/119Sn) = 319 Hz, 1J(119Sn – 13Ci) = 553 Hz, Sn2),
42 ppm (1Sn, 2J(119Sn – 117/119Sn) = 319 Hz, Sn1). Anal. Calcd (%) for C39H36I4Sn4: C
31.5, H 2.44. Found: C 31.4, H 2.5. Electrospray MS: m/z (%) positive mode 1169.0
C21H31I3O2Sn4+ (100, [M – I– – 3Ph– + 3H2O + 4H+]+), 1250.9 C27H37I3O2Sn4+ (50,
[M – Ph– – I– + 2H2O + 3H+]+).
• Synthesis of ClSn(CH2SnPh2Cl)3 (5)
To a solution of 4 (0.416 g, 0.280 mmol) in CH2Cl2 (40 mL) was added excess of silver
chloride (0.16 g, 1.12 mmol). The resulting mixture was stirred at room temperature in
the dark for 14 days. The formed AgI and the non-reacted AgCl was removed by filtration.
The CH2Cl2 of the filtrate was evaporated in vacuo (10−3 mmHg) to afford a yellowish oily
substance in 70 % yield (0.219 g, 0.195 mmol). No purification by column chromatography
could be realized given the instability of such compounds. No crystalline material was
isolated.
1H NMR (CDCl3, 300.13, 298 K): δ 1.3 ppm (s, 6H, 2J(1H – 117/119Sn) = 72 Hz,
Sn1CH2Sn2), 7.44- 7.75 ppm (complex pattern, 30H, Ph). 119Sn NMR (CDCl3, 111.92,
298 K): δ 17 ppm (3Sn, Sn2), 151 ppm (1Sn, Sn1).
Complexation studies
• Formation of (PPh4)[CH2(SnCl2Ph)2 ·Cl] (6), and
(PPh4)2[Cl2Sn(CH2SnCl2Ph)2 ·2Cl] (7)
Tetraphenylphosphonium chloride (21.44 mg, 0.057 mmol) is added to a solution of 3
(57 mg, 0.057 mmol) in 20 mL CH2Cl2 and the mixture is stirred at room tempera-
ture overnight. The solvent is evacuated to afford a white solid. Re-crystallization from
111
3. The Spacer-Bridged Tetrastannanes R'Sn(CH2SnR(3 –n) Xn)3, (n = 0– 2; X = I, Cl; R =
Ph, R'= R, X), Syntheses, Structures and Complexation Studies
dichloromethane/ iso-hexane give two types of colourless crystals 6 and 7 as fragmentation
products.
119Sn NMR (CDCl3, 149.26, 298 K): (crude mixture) δ 117 ppm (24 %), -75 ppm (15 %),
-32 ppm (36 %), and the starting material 3: δ –28 and -54 ppm (23 %). Electrospray MS
for 6: m/z (%) negative mode 582.8 [CH2(SnCl2Ph)2 ·Cl]– (100,[ M – (PPh4)+]– ), m/z
(%) positive mode 339.1 (100, PPh4+). Anal. Calcd (%) for 6: C37H34Cl5PSn2 + 2H2O:
C 46.28, H 3.99. Found: C 46.2, H 3.7. Anal. Calcd (%) for 7: C62H55Cl8P2Sn3 + H2O +
CH2Cl2: C 47.15, H 3.71. Found: C 47.3, H 3.6. No further investigations could be realized
within the time frame of this PhD, given the luck of material and the difficulties to separate.
• Formation of (PPh4)2[CH2(SnCl2Ph)2 ·2Cl] (8)
Tetraphenylphosphonium chloride (58.69 mg, 0.156 mmol) is added to a solution of 3
(39 mg, 0.039 mmol) in 20 mL CH2Cl2 and the mixture is stirred at room tempera-
ture overnight. The solvent is evacuated to afford a white solid. Re-crystallization from
dichloromethane/ diethyl-ether give colourless crystals 8 as fragmentation product.
119Sn NMR (CDCl3, 149.26, 298 K): (crude mixture) δ –250 ppm (16 %), -179 ppm
(23 %), -141 ppm (40 %), and -59 ppm (19 %). Anal. Calcd (%) for: C61H55Cl6P2Sn2 +
2H2O: C 54.8, H 4.4. Found: C 54.8, H 4.1. No further investigations could be realized
within the time frame of this PhD, given the luck of material and the difficulties to separate
different fragmentation products.
• Formation of (C5H6N)2[CH2(SnCl2Ph)2 ·2Cl] (9)
Pyridinium chloride (7.42 mg, 0.064 mmol) is added to a solution of 3 (64 mg, 0.064
mmol) in 20 mL CH2Cl2 and the mixture is stirred at room temperature overnight. The
solvent is evacuated to afford a white solid. Re-crystallization from dichloromethane/
diethyl-ether give colourless crystals 9 as fragmentation product.
119Sn NMR (CDCl3, 149.26, 298 K): (crude mixture) δ –95 ppm (7.5 %), -28 ppm
(29.4 %), -5 ppm (37 %), 46 ppm (6 %), and 56 ppm (20 %). 119Sn NMR (CDCl3,
149.26, 298 K): δ –30 ppm (W1/2 = 200 Hz). Electrospray MS: m/z (%) positive
mode 841.1 C25H33Cl6N3OSn2+ [60, M + CH3CN + H2O + H+]+. Anal. Calcd (%) for:
C23H27Cl6 N2Sn2 + H2O: C 34.55, H 3.66. N 3.5 Found: C 34.5, H 3.9, N 3.8. No further
investigations could be realized within the time frame of this PhD.
112
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph ,
CH2SiMe3) as Precursors for Unprecedented Diorgan-
otin Oxo Clusters and Adamantane-like Structures
4.1 Introduction
Over the last decade, we witnessed the global growing interest for the studying of macro-
cycles containing transition-metal group elements versus a luck of such supramolecular
architectures either as macrocycles or coordination polymers presenting in their skeletons
main[39]group elements, especially Tin (II) and Tin (IV) compounds. So far such macro-
cycles and extended network structures have been reported only for a limited number, and
most of them are triorganotin derivatives. This is explained by the requirement of a subtle
balance of electronic and steric effects of the organic groups attached to the tin and ligand
moieties.[40]
It is common knowledge that the complete replacement of the electronegative substituents
X in diorganotin compounds of type R2SnX2 (X = halogen, alkoxide, carboxylate) with
oxide dianion gives the corresponding diorganotin oxides (R2SnO)n. Depending on the
identity of the organic substituents R, these oxides can either be polymeric (type I, n =
∞),[41] trimeric (type II, n = 3)[23,42,43] or even dimeric (type III, n = 3) (Chart 2).[39,44]
Sterically less demanding organic substituents such as n-alkyl or phenyl give polymers
which, as a result of intermolecular OSn interactions making the tin atoms five-or even
six-coordinate, are almost insoluble in common organic solvents. Increasing the steric
bulk of the organic substituents enables the formation of six- or even four-membered rings
in which the tin atoms are four-coordinate. The same principle holds for the formation
of the molecular diorganotin oxides of types IIa (in which two parallel six-membered
Sn3O3 rings are linked to each other by three organic spacers),[43] IV (adamantane-type
structure),[19] and V (the only chrystallographically characterized diorganotin oxide con-
taining an eight-membered Sn4O4 ring).[19] More recently, intramolecular NSn or P =
OSn coordination proved to be alternatives to steric bulk for the stabilization of type
III diorganotin oxides. (Chart 2).[44,45]
Herein, we report that even diorganotin compounds containing sterically less-crowded
substituents (Ph, Me3SiCH2) but having a particular tripod architechture compounds
MeSi(CH2SnR(3 –n) Xn)3 give a new serie of ladder-containing oxo clusters, among which
113
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
cyclic polynuclear molecular diorganotin oxides of unprecedented large sizes in which
the tin atoms adopt the coordination number five. These are the two first and longest
simple ladder- containing macrocycles with 18 and 30 Tin centers, linked to each other
through planar Sn2 – O2 rings and assembled without linking bridges, as it is known in
literature for such polymeric structures.[46] There is also formation of first S- and Se-
containing adamantane-type structures, in which both organosilicon and organotin moi-
eties are present. The numbering of compounds in this Chapter follows consecutively the
numbering in chapter 2.
Chart 2. Different types of diorganotin oxides.[45]
Sn
O
Sn
Sn
O
Sn
OO
R
RR
R
Y
Sn
O
Sn
Y
Sn
O
Sn
O O
R
R R
R
IV: R = CH(SiMe3)2; Y = CMe2, (CH2)2
IIa: Y = C6H4(SiMe2CH2)2-1,4;
     R = CH(SiMe3)2
(R2SnO)n
I:  R = Me, Et, n-Bu, Ph...; n =
V: R = CH(SiMe3)2
[MeSi(CH2SnRO)3]n
VI: R = Ph, n = 6; R = CH2SiMe3, n = 10, 
  (this work)
O
Sn
O
Sn
R
R
R
R
III: R = R' = CH(SiMe3)2,
R = {2,6-P(O)(O i-Pr)2}2-4-t-BuC6H2, R' = Et,
   R = 2,6-(Me2NCH2)2C6H3, R' = n-Bu;
O
Sn
O
Sn
O
Sn
R R
R
R
R
R
II:  R = t-Bu,Me3SiCH2,CEtMe2, 
   CSiMe3/Me,2,6-Me2-C6H3,
   2,6-Et2-C6H3,2,4,6-(CF3)3-C6H2,
2,4,6-i-Pr-C6H2;
O
Sn O Sn
OSn
O
Sn O Sn
OSn
Y
R
R
R
Y
R R
R
Y
114
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
4.2 New ladder-type containing diorganotin oxo-clusters
A 119Sn NMR of the crude mixture resulting from a reaction of the organotin hexachlo-
rido derivative MeSi(CH2SnPhCl2)3, 4, with one molar equiv di-tert-butyltin oxide (t-
Bu2SnO)3 in CDCl3, shows resonances from δ –331 ppm to -54 ppm, with six major
signals at δ –230 (5 %), -201 (6 %), -192 (6 %), -117 (4 %), -100.6 (7 %), and 54 ppm
(44 %). The latter signal refers to the by-product t-BuSnCl2. There are also minor sig-
nals appearing from δ –331 to –100.3, with integrations varying between 0.3-1.2 %. (See
Supporting Information Chapter 4, Figure S7) After several washings with iso-hexane of
the white residue resulting from the reaction mixture after the solvent had been evapo-
rated in vacuo, and recrystallization from dichloromethane/iso-hexane gives compound
26, [(MeSi(CH2)3)Sn(µ3-O)3(Ph)Sn(Cl)(Ph)Sn(µ2-OH)(Ph)Sn(t– Bu)2]2, (Scheme 20) as
colourless crystals suitable for X-Ray diffraction study.
Scheme 20. Synthesis of the octanuclear ladder-like oxocluster 26.
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
Si
Me
Sn
Sn
Sn
O O
Ph
O
SnO t-Bu
t-BuCl
O
Sn
t-Bu Cl
t-Bu
O
Ph
Ph
Sn Sn
SnO
O
Ph
Ph
Ph
Si
Me
2
2 (t-Bu2SnO)3, 2 H2O
CHCl3
−4 (t-Bu2SnCl2)
 −2 HCl
+
further unknown species
4 26
H
H
The molecular structure of 26 is shown in Figure 46, selected interatomic distances and
angles are listed in the figure caption. It shows a centrosymmetric dimer containing four
crystallographically independent tin atoms (Sn1, Sn2, Sn3 and Sn4), (Figures 46, 49). The
ladder-like structure consists of four 6-membered-rings (Si – C – Sn – O – Sn – C) and seven
4-membered Sn2O2-rings.
115
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 46. POV-Ray image of the molecular structure of
[(MeSi(CH2)3)Sn(µ3-O)3(Ph)Sn(Cl)(Ph)Sn(µ2-OH)(Ph)Sn(t-Bu)2]2, 26. The proton
at the oxygen atom O1 was not found on the electron density map. Selected interatomic
distances (Å): Sn(1)–O(1) 2.140(4), Sn(4A)–O(1) 2.220(5), Sn(2)–O(2) 2.078(4),
Sn(3A)–O(2) 2.036(5), Si(1)–C(1) 1.879(7), Si(1)–C(2) 1.858(7), Si(1)–C(3) 1.855(7),
C(1)–Sn(1) 2.126(7), C(2)–Sn(2) 2.154(7), C(3)–Sn(3) 2.121(7). Selected interatomic
angles (◦): O(4A)–Sn(1)–O(2) 75.02(17), O(4A)–Sn(1)–C(11) 121.9(2), O(2)–Sn(1)–
C(11) 98.0(2), O(4A)–Sn(1)–C(1) 117.9(2), O(2)–Sn(1)–C(1) 97.8(2), C(11)–Sn(1)–C(1)
120.2(3), O(3)–Sn(2)–O(3A) 76.20(19), O(3)–Sn(2)–C(21) 116.1(2), O(3A)–Sn(2)–C(21)
95.8(2), O(3)–Sn(2)–C(2) 94.2(2), O(3A)–Sn(2)–C(2) 150.4(2), O(21)–Sn(2)–C(2)
113.5(3), O(2)–Sn(3A)–C(3A) 117.1(3), O(2)–Sn(3A)–C(31A) 112.0(2), C(3A)–Sn(3A)–
C(31A) 130.9(3), O(2)–Sn(3A)–O(3A) 74.63(18), C(3A)–Sn(3A)–O(3A) 95.6(2),
C(31A)–Sn(3A)–O(3A) 96.8(2), O(4A)–Sn(4A)–C(45A) 114.2(2), O(4A)–Sn(4A)–
C(41A) 121.7(2), C(45A)–Sn(4A)–C(41A) 123.2(3), O(4A)–Sn(4A)–O(1) 73.69(17),
C(45A)–Sn(4A)–O(1) 92.4(2), C(41A)–Sn(4A)–O(1) 94.0(2), Si(1)–C(1)–Sn(1) 120.1(3),
Si(1)–C(2)–Sn(2) 113.5(3), Si(1)–C(3)–Sn(3) 121.2(4).
Both the endo-cyclic and exo-cyclic tin atoms exhibit a distorted trigonal bipyramidal
environment with the equatorial positions being occupied by two carbon atoms and one
116
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
oxygen atom [C(1), C(11), O(4A) for Sn(1)], [C(2), C(21), O(3A) for Sn(2)], [C(3A),
C(31A), O(2) for Sn(3A)], and [C(41A), C(45A), O(4A) for Sn(4A)] (Figure 47).
Sn(1)
O(2)
C(1)
O(4A)
C(11)
O(1)
Sn(2)
O(3)
C(2)
O(3A)
C(21)
O(2)
Sn(3A)
O(3A)
C(3A)
O(2)
C(31A)
O(4A)
Sn(4A)
O(1)
C(41A)
O(4A)
C(45A)
Cl(1A)
Figure 47. Configuration of the trigonal bipyramidal endo-tin atoms Sn(1), Sn(2) and
Sn(3A) and the exo-cyclic tin atom Sn(4A) of compound 26.
For the endocyclic tin atoms, the axial positions are occupied by two oxygen atoms [O(2),
µ2-O(1) for Sn(1)], [O(3), O(2) for Sn(2)], [O(3A),O(4A) for Sn(3A)]. For the exocyclic
tin atom Sn(4A), the axial positions are occupied by µ2–O(1) and Cl(1A) (Figure 47). The
geometrical goodnesses[22] are ∆Σ(θ) = 89.2◦ for Sn(1) , 73.2◦ for Sn(2), 92.6◦ for Sn(3A),
and 80.1◦ for Sn(4A). Notably, ∆Σ(θ) of Sn3A is higher than 90◦, this is probably due
to the distortion of the angles (C3A – Sn3A – C31A) 130.9(3)◦ and (C31A – Sn3A – O4A)
100.9(2)◦ from the ideal geometry, respectively, 120 and 90◦.
The Sn–O interatomic distances range between 2.036(5) and 2.220(5) Å. The
Snendo – µ2 – O – Snexo bridges are unsymmetrical with Sn(1) – O(1) 2.140(4) Å and
Sn(4A) – O(1) 2.220(5) Å. This data is typical for such ladder-like compounds.[20,22,23]
The Si(1) – C(1) – Sn(1), Si(1) – C(2) – Sn(2) and Si(1) – C(3) – Sn(3) angles are 120.1(3),
113.5(3), and 121.2(4)◦. As the matter of fact, we observe in compound 26 the
Sn4O2X2Y2-structural motif, (X, Y = OH, Cl), characteristic for tetraorganodistannox-
anes.[23,47,48] This motif is presented as Sn4O6OH2Cl2, exhibiting an unymmetrical
combination, in which the hydroxy groups are located in the bridging positions and the
chlorine atoms are bonded to the exocyclic tin atoms. This can be due to a competition
between the different donor strength of OH and Cl. It is well-known that OH has a
higher bridging capacity than Cl. To conclude, the ladder-like compound 26 present-
ing the structural motif [Ph3(MeSi(CH2)3)Sn(µ3-O)3SnClSn(µ2-OH)Sn(t– Bu)2],
resembles [t– Bu2(µ2-OH)Sn(µ3-O)SnCl(CH2Si(Me)3)2],
[t– Bu2(µ2-OH)Sn(µ3-O)SnPh(CH2(Me)2SiO)Sn – t– Bu2(µ3 – O)][22] and related
compounds. Comparing to the first example we extended the silicon methylene-bridged
117
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
tin arms to have four more Sn–O bridges and concerning the second example, we have
one more Sn2O2 ring due to the third silicon methylene-bridged tin arm missing in this
later. Compound 26 is the first octanuclear simple ladder-like organotin tin oxo cluster. In
fact, referring to the Cambridge Structural Data Base, only a maximum of hexanuclear
simple ladder-like tin oxo clusters having different features such as open-drum structures
were reported until now.[16, 17, 49]
The identity of compound 26 is retained in solution. The compound is kinetically inert
on the 1H, 13C, 29Si and 119Sn NMR time scales. Thus, a 1H NMR spectrum (C6D6
solution, Figure 48) shows two resonances referring to four t-Bu2 groups at δ 1.07
(3J(1H – 117/119Sn) 116 Hz; integral 18) and 1.63 (3J(1H – 117/119Sn) 116 Hz; integral 18)
ppm. The resonance signal of the SiCH3 protons appears at δ 0.78 ppm (integral 6). The
SiCH2 protons, with integration each of 2H, appear as equally intense AX-type resonances
at δ –0.075 (2J(1H – 117/119Sn) = 81 Hz, 2J(1H – 1H) = 13 Hz), 0.215 (2J(1H – 117/119Sn)
= 68 Hz, 2J(1H – 1H) = 13 Hz), 0.52 (2J(1H – 117/119Sn) = 80 Hz, 2J(1H – 1H) = 13 Hz),
0.805 (2J(1H – 117/119Sn) not measured, 2J(1H – 1H) = 13 Hz), 2.17 ppm (2J(1H – 117/119Sn)
= 126 Hz, 2J(1H – 1H) = 13 Hz), 2.37 (2J(1H – 117/119Sn) = 106 Hz, 2J(1H – 1H) = 13 Hz).
The complex pattern referring to the phenyl protons appears at δ 6.98-8.27 ppm with
integration of 30H (See Supporting Information Chapter 4, Figures S1-S3). In a 13C NMR
spectrum (C6D6 solution, see Supporting Information Chapter 4, Figures S4- S6), the res-
onances corresponding to SiCH3 at δ 5.5 ppm (1J(13C – 29Si) = 74 Hz, 3J(13C – 117/119Sn)
= 53 Hz) and those of SiCH2Sn at δ 7.6, 11.4, 18.1, 41.4, 42.0 ppm with coupling con-
stants, respectively, equal to 1J(13C – 117/119Sn) = 464, 517, 503, 568, and 576. The reso-
nances corresponding to the t-Bu groups appear at 30.5 (C(CH3)3), 31.02(C(CH3)3), and
31.6 (C(CH3)3), 31.9 (C(CH3)3) ppm. In the aromatic part, there are three signal reso-
nances referring to each carbon of the phenyl groups, indicating that there are three non-
equivalent tin atoms coordinated to the phenyl groups; Cm (δ 128.7, 128.8, 128.9 ppm), Cp
(δ 130.2, 130.26, 130.47 ppm, 4J(13C – 117/119Sn) = 14 Hz), Co (δ 136.2, 136.7, 137.1 ppm,
2J(13C-117/119Sn) = 59 Hz), and Ci (δ 143.9, 144.61, 144.67 ppm, 1J(13C – 117/119Sn) =
759/805 Hz).
A 119Sn NMR spectrum of a solution in CDCl3 of a crystalline sample of
26 (Figure 49) shows four resonances with equal ratio; 1:1:1:1 at δ –195
(Sn3A) (2J(119Sn3A – 117/119Snexo) = 298 Hz, 2J(119Sn3A – 117Snendo) = 180 Hz,
2J(119Sn3A – 29Si) = 62 Hz), -208 (Sn2) (2J(119Sn2 – 117/119Snendo) = 243 Hz,
2J(119Sn2 – 117Snendo) = 90 Hz) and two very close resonances at δ –228 ppm
(Sn1) (2J(119Sn1 – 117/119Snexo) = 285 Hz, 2J(119Sn2 – 117/119Snendo) = 209 Hz,
2J(119Sn1 – 117Snendo) = 99 Hz) and -230 ppm (Sn4A). Sn1, Sn2 and Sn3A are en-
docyclic tin atoms whereas Sn4A is exocyclic. These four signal resonances correspond
to four non-equivalent tin atoms, which matches perfectly with the molecular structure
118
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
found in the solid state. The chemical shifts indicate that all tin atoms are pentaco-
ordinated.[22,23,47] This underlines the stability of 26 in solution, which is rather rare
for such organotin oxo clusters.[22,50] An ESI-MS spectrum (positive mode) of 26
shows one intense mass cluster centred at m/z 2012.7485 corresponding to the cation
[C60H87Cl2O8Si2Sn8]+ ([M + H]+), which confirms that the cluster remains intact
in solution even under harsh ESI-MS conditions. Finally, an IR spectrum shows an
absorption band at ν 2924-2849 cm−1 corresponding to OH groups (See Supporting
Information Chapter 4, Figures S11–S14). However, referring to the crystallographic
study, the protons at the oxygen atom O(1) and O(1A) were not found in the electron
density map. The presence of hydroxy groups in such position is rather typical for similar
compounds.[22,23]
119
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 48. 1H NMR spectrum (600.29 MHz, C6D6) of crystals sample of 26: hole spec-
trum and aliphatic part are shown.
120
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 49. 119Sn NMR spectrum (223.85 MHz, CDCl3) of crystals sample of 26.
The reaction of the hexachlorido-derivative MeSi(CH2SnCH2SiMe3Cl2)3, 12, with
one molar equiv di-tert-butyltin oxide (t-Bu2SnO)3 in CHCl3 give a white solid
material which is soluble in CH2Cl2 and CH3Cl · ..A 119Sn NMR spectrum in C6D6
of this material shows signals from δ –242 ppm to -29 ppm, with major signals at
δ –82 ppm (25.2 %) and -29 ppm (22 %), referring, respectively to the remaining
reagent cyclo-(t-Bu2SnO)3, and (t-Bu2SnOHCl)2 as by-products. The other reso-
nances appear at -242 (5.8 %), -228 (12 %), -222 (9 %), -146 (6.5 %), -139 (6 %),
121
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
and -124 (13.3 %) ppm (See Supporting Information, Chapter 4, Figure S18). After
several washings of this white residue resulting from the reaction mixture, with
iso-hexane, recrystallization from dichloromethane/iso-hexane gives compound 27,
{[MeSi(CH2)3]SnCl(CH2SiMe3)(µ3-O)SnCl(CH2SiMe3)Sn(µ3-O)(Cl)2(CH2SiMe3)Sn(t-Bu)2},
(Scheme 21) as colourless single crystals suitable for X-ray diffraction study.
Scheme 21. Synthesis of the tetranuclear ladder-like diorganotin oxocluster 27.
Si
Me
Sn
Sn
Sn
Cl
Cl
Me3SiH2C
Me3SiH2C
Cl
Cl
CH2SiMe3
Cl
Cl
12
(t-Bu2SnO)3, Η2Ο
CHCl3
− (t-Bu2SnOHCl)2
further unknown species
+
27
Si
Sn
Sn
Sn
Cl
O
Cl
Me
Cl
Sn
t-Bu
t-Bu
Cl
O SiMe3
Me3Si
SiMe3
Figure 50 shows the molecular structure of 27 and the figure caption contains se-
lected interatomic distances and angles. It shows a typical planar Sn4Cl4O2 layer
with a central Sn2O2 ring characteristics of a ladder-like structure. This is due to
OSn and ClSn intramolecular coordination. This structure is very similar to that
of {[(R(Cl)Sn(CH2)3Sn(Cl)(CH2)2SiMe2]O2}2, R = CH2SiMe3,[20] only this latter is a
double ladder dimer interconnected with four trimethylene chains. As to compound 27 is
a simple ladder monomeric structure, which, can be considered, with caution as a mod-
ified adamantane-type structure [MeSi(CH2SnCH2SiMe3)3OCl2] in coordination with a
µ3-oxygen atom, that can be issued from the reagent t-Bu2SnO or from H2O present un-
der the experiment conditions and a t-Bu2SnCl2 molecule resulting from the reaction
between compound 12 and the reagent t-Bu2SnO (Scheme 22). Different perspectives of
this adamantine-like structure are shown in Figure 51. Consequently, compound 27 con-
tains four crystallographically independent tin atoms (Sn1, Sn2, Sn3 and Sn4) (Figure 50).
This is also the case for the similar compound mentioned above.[20]
122
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 50. POV-Ray image of the molecular structure of
{[MeSi(CH2)3]SnCl(CH2SiMe3)(µ3-O)SnCl(CH2SiMe3)Sn(µ3-O)(Cl)2 (CH2SiMe3)
Sn(t-Bu)2}, 27. Selected interatomic distances (Å): Sn(1)–O(1) 2.031(6), Sn(2)–Cl(2)
2.994(3), Sn(2)–Cl(3) 2.964(3), Sn(2)–O(1) 2.108(6), Sn(2)–O(2) 2.072(6), Sn(3)–Cl(1)
3.011(3), Sn(3)–Cl(4) 2.925(3), Sn(3)–O(1) 2.102(6), Sn(3)–O(2) 2.073(6), Sn(4)–
O(2) 2.040(6), Sn(1)–Cl(1) 2.576(3), Sn(1)–Cl(2) 2.560(3), Sn(4)–Cl(3) 2.609(2),
Sn(4)–Cl(4) 2.620(3). Selected interatomic angles (◦): O(2)–Sn(2)–Cl(2) 147.24(18),
O(1)–Sn(2)–Cl(3) 145.86(17), Cl(2)–Sn(2)–Cl3) 142.38(7), O(1)–Sn(2)–C(21) 104.9(3),
O(2)–Sn(2)–C(21) 108.1(3), C(2)–Sn(2)–C(21) 148.8(3), O(1)–Sn(3)–Cl(4) 147.58(18),
O(2)–Sn(3)–Cl(1) 146.58(17), Cl(1)–Sn(3)–Cl(4) 141.66(7), O(1)–Sn(3)–C(31) 102.2(3),
O(2)–Sn(3)–C(31) 109.4(3), C(3)–Sn(3)–C(31) 149.5(4), C(1)–Sn(1)–C(11) 136.2(4),
Cl(2)–Sn(1)–C(11) 92.9(3), Cl(2)–Sn(1)–C(1) 92.5(3), C(45)–Sn(4)–C(41) 126.5(4),
O(2)–Sn(4)–Cl(3) 78.62(18), C(45)–Sn(4)–Cl(3) 101.4(3), Si(1)–C(1)–Sn(1) 111.6(5),
Si(1)–C(3)–Sn(3) 115.1(5).
123
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 51. Different perspectives of the adamantine-like structure
[MeSi(CH2SnCH2SiMe3)3(O)Cl2] coordinated with µ3-O and a t-Bu2SnCl2 molecule.
Sn(2) and Sn(3) are incorporated in the central four-membered Sn2O2-ring as for Sn(1)
and Sn(4) are bonded exocyclic to this ring. The endo-cyclic Sn atoms are hexa-
coordinated and exhibit each a distorted octahedral all-trans SnC2Cl2O2 environment at
Sn(2) and Sn(3) with angles of (O2–Sn2–Cl2) 147.24(18)◦, (O1–Sn2–Cl3) 145.86(17)◦,
(Cl2–Sn2–Cl3) 142.38(7)◦, (O1–Sn2–C21) 104.9(3)◦, (O2–Sn2–C21) 108.1(3)◦, (C2–
Sn2–C21) 148.8(3)◦, (O1–Sn3–Cl4) 147.58(18)◦, (O2–Sn3–Cl1) 146.58(17)◦, (Cl1–Sn3–
Cl4) 141.66(7)◦, (O1–Sn3–C31) 102.2(3)◦, (O2–Sn3–C31) 109.4(3)◦, (C3 – – Sn3 – – C31)
149.5(4)◦. The chlorido– and the oxido– bridges; Cl–Snendo–Cl and O–Snendo–O are
unsymmetrical at Sn(2) and Sn(3) with Sn(2)–Cl(2), Sn(2)–Cl(3), Sn(2)–O(1), Sn(2)–
O(2), Sn(3)–Cl(1), Sn(3)–Cl(4), Sn(3)–O(1), Sn(3)–O(2), distances of 2.994(3), 2.964(3),
2.108(6), 2.072(6), 3.011(3), 2.925(3), 2.102(6), and 2.073(6) Å, respectively. These dis-
tances prove, however, that the Snendo-µ3-O-Snendo bridges are approximately equal. This
affirmation is typical for such ladder-like compounds.[20,22,23] The exo-cyclic tin atoms
Sn(1) and Sn(4) exhibit a distorted trigonal bipyramidal environments, in which Sn(1) is
coordinated to two CH2SiMe-groups, two chlorine and one oxygen atoms, as to Sn(4) is
coordinated to two t-Bu- groups, two chlorine and one oxygen atoms, with the equatorial
124
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
positions being occupied by two carbon atoms and one oxygen atom (C(1), C(11), O(1)
for Sn(1)), (C(41), C(45), O(2) for Sn(4)).
As to the axial positions, are being occupied by two oxygen atoms (Cl(1), Cl(2) for Sn(1)),
(Cl(3), Cl(4) for Sn(4)), (O(3A),O(4A) for Sn(3A)). The geometrical goodnesses ∆Σ(θ)[22]
are equal to 92.1◦ for Sn(1) and 87.9◦ for Sn(4). Notably, ∆Σ(θ) of Sn1 is higher than 90◦,
this is probably due to the distortion of the angles (C1–Sn1–C11) 136.2(4)◦, (Cl2–Sn1–
C11) 92.9(3)◦, and (Cl2–Sn1–C1) 92.5(3)◦ from the ideal geometry, respectively, 120 and
90◦. This distortion from the ideal geometry is mainly the result of the Cl(1) and Cl(2)
atoms intramolecularly approaching Sn(2) and Sn(3).
The Sn–O interatomic distances range between 2.031(6) and 2.108(6) Å, as to the Sn–Cl in-
teratomic distances range between 2.560(3) and 3.011(3). The Snendo-(µ3-O)-Snexo bridges
are unsymmetrical with distances of Sn(1) – O(1) 2.031(6) Å, Sn(2)–O(1) 2.108(6) Å,
Sn(3) – O(1) 2.102(6) Å, Sn(2) – O(2) 2.072(6) Å, Sn(4) – O(2) 2.040(6) Å, Sn(3) – O(2)
2.073(6) Å. As to the Snendo-Cl-Snexo bridges are unsymmetrical with distances of
Sn(1) – Cl(1) 2.576(3) Å, Sn(3) – Cl(1) 3.011(3) Å, Sn(1) – Cl(2) 2.560(3) Å, Sn(2) – Cl(2)
2.994(3) Å, Sn(2) – Cl(3) 2.964(3) Å, Sn(4) – Cl(3) 2.609(2) Å, Sn(3) – Cl(4) 2.925(3) Å,
Sn(4) – Cl(4) 2.620(3) Å.
Bond distances and angles around the silicon methylene-bridged organotin arms
Si(1) – C(1) – Sn(1), Si(1) – C(2) – Sn(2) and Si(1) – C(3) – Sn(3) are almost equal. The cor-
responding angles vary between 111.6(5)◦ (Si1–C1–Sn1), 115.1(5)◦ (Si1–C3–Sn3). This
statement refers to the tripod geometry characteristic of these novel organotin precursors.
A close inspection of the interatomic distances support the interpretation of the solid state
structure as it is schematically shown in Scheme 22. The central Sn2O2 four-membered
ring is coordinated by one t-Bu2SnCl2 and the remaining CH2SnCl2R (R = CH2SiMe3)
substituent attached to the bridgehead MeSi silicon atom. The situation resembles that
reported for the unsymmetrical tetraorganodistannoxane (t-Bu2ClSnOSnClMe2)2.[51]
125
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Scheme 22. Schematic drawing of the solid-state structure of compound 27.
Si
Sn
Sn Sn
Cl
O
Cl
Me
Si
Sn
Sn
Sn
Cl
O
Cl
Me
Cl
Sn
t-Bu
t-Bu
Cl
O SiMe3
Me3Si
SiMe3
SiSi
Si
  t-Bu2SnO(in solution)
(in solid state)
t-Bu2SnCl2
Si
Sn
Sn
Sn
Cl
O
Cl
Me
Cl
Sn
t-Bu
t-Bu
Cl
O
SiMe3
Me3Si
SiMe3
The solid state structure of 27 is retained in solution. Thus, a 119Sn NMR spectrum of
a solution in C6D6 of a crystalline sample of 27 (See Supporting Information, Chap-
ter 4, Figure S19) shows four signal resonances with equal ratio; 1:1:1:1 at δ –218 re-
ferring to the exocyclic Sn(4) atom (2J(119Sn4 – 117/119Snendo) = 208 Hz), -149 ppm re-
ferring most probably to the second exocyclic Sn(1) atom (2J(119Sn1 – 117/119Snendo))
= 214 Hz), given the almost equal 2J(119Snexo – 117/119Snendo) coupling constants, and
two resonance signals referring to the endocyclic Sn atoms Sn(2)/Sn(3) at δ –158 ppm
126
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
(2J(119Snendo – 117Snendo) = 125 Hz) and δ –132 ppm. These four signal resonances corre-
spond to four non-equivalent tin atoms which matches perfectly with the molecular struc-
ture found in the solid state. This is the same case as the resembling dimeric compound
{[(R(Cl)Sn(CH2)3Sn(Cl)(CH2)2SiMe2]O2}2, R = CH2SiMe3.[20] A 29Si NMR spectrum
(See Supporting Information, Chapter 4, Figure S17) of this sample matches perfectly
with the previous statement. There are three resonance signals at 0.81, 1.3, and 1.5 ppm
referring to the CH2SiMe3 silicon atoms bound to three non-equivalent Sn atoms. The
resonance for the SiMe appears at -21 ppm. This also underlines the stability of 27 in
solution, which is rather rare for such organotin oxo clusters.[22,50]
A 1H NMR spectrum (C6D6 solution, see Supporting Information, Chapter 4, Figure S16)
confirms, as well the retention of the solid-state structure of 27 in solution. It shows two
resonances referring to two t-Bu2 groups at δ 1.38 and 1.41 (integral 18H). The resonance
signals corresponding to SiCH3 protons of the head SiMe and the CH2SiMe3 groups
appear as a complex pattern at δ 1.24–1.36 ppm (integral 30H). The SiCH2 protons appear
as three resonance signals at δ 0.21, 0.26, and 0.27 ppm with integration of 12H. The
coupling constants are difficult to identify due to the quality of the NMR spectrum. No
further measurements could be done within the time frame of this PhD.
An ESI-MS spectrum (positive mode, see Supporting Information, Chap-
ter 4, Figure S20- 22) of 27 shows two intense mass clusters cen-
tred at m/z 793.1270, and 807.1418 corresponding, respectively, to the
cation [C16H45Cl2OSi4Sn3]+{[MeSi(CH2SnCH2SiMe3)3(O)Cl2] + H+}+ and
[C16H44Cl2O2Si4Sn3]+ {[MeSi(CH2SnCH2SiMe3)3(O)Cl2] + (µ3-O)}+. These two
mass clusters refer to the formation of adamantane-like structure in solution, suggested in
Scheme 22 and support, with caution, the ring-opening mechanism as a formation path of
27.
The reaction of the hexaiodido derivative MeSi(CH2SnCH2SiMe3I2)3, 11, with
one molar equiv cyclo-(t-Bu2SnO)3 in CHCl3 gives a white solid material solu-
ble in almost all halogenated organic solvents. A 119Sn NMR spectrum in CDCl3
solution of this material, , shows one resonance signal at δ 62 ppm (51 %), corre-
sponding to the by-product t-Bu2SnI2, and three resonances at -183.8, -156, and
-150 ppm with a sum integration of 49 % (See Supporting Information, Chap-
ter 4, Figure S27). After several washings of this white solid material with iso-
hexane, recrystallization from dichloromethane/iso-hexane gives compound 28,
{[MeSi(CH2)3]SnI(CH2SiMe3)(µ2-OH)[SnO(CH2SiMe3)]2Sn(µ2-OH)ISn(t-Bu)2},
(Scheme 23) as colourless single crystals suitable for X-Ray diffractometer study.
127
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Scheme 23. Synthesis of the tetranuclear ladder-like diorganotin oxocluster 28.
11
(t-Bu2SnO)3
CHCl3
2(t-Bu2SnI2)
28
Si
Me
Sn
Sn
Sn
I
I
Me3SiH2C
Me3SiH2C
I
I
CH2SiMe3
I
I
Si
Sn
Sn
Sn
O
O
O
Me
I
Sn t-Bu
t-Bu
O
SiMe3
SiMe3
SiMe3
I
H
H
Figures 52 and 53 show the molecular structure of 28 and the figure caption contains
selected interatomic distances and angles.
Figure 52. POV-Ray image of the molecular structure of
{[MeSi(CH2)3]SnI(CH2SiMe3)(µ2-OH)[SnO(CH2SiMe3)]2Sn(µ2-OH)I Sn(t-Bu)2},
28. Selected interatomic distances (Å): Sn(1)–O(1) 2.036(2), Sn(2)–O(1) 2.048(2),
Sn(3)–O(1) 2.157(2), Sn(1)–O(3) 2.175(3), Sn(2)–O(3) 2.195(3), Sn(2)–O(2) 2.138(2),
Sn(4)–O(2) 2.033(2), Sn(4)–O(4) 2.196(3), Sn(3)–O(4) 2.176(3), Sn(1)–I(1) 2.9508(3),
Sn(4)–I(2) 2.9173(4). Selected interatomic angles (◦): (C1–Sn1–C5) 122.82(14), (O3–Sn1–
I1) 157.55(7), (O3–Sn1–O1) 73.30(9), O(1)–Sn(2)–O(2) 76.03(9), O(1)–Sn(2)–C(10)
101.75(12), O(2)–Sn(2)–O(3) 148.46(9), (O2–Sn3–C16) 115.05(12), (O2–Sn3–O1)
75.39(9), (O1–Sn2–O4) 149.06(9), C(20)–Sn(4)–C(21) 142.82(14), O(4)–Sn(4)–I(2)
164.16(7), O(2)–Sn(4)–I(2) 89.98(7).
128
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 53. Different perspectives of the the adamantine-like structure
[MeSi(CH2SnOCH2SiMe3)3] coordinated with one H2O and a t-Bu2SnI2 molecules.
Compound 28 crystallizes in the monoclinic space group P21/n. It contains four crystal-
lographically independent tin atoms (Sn1, Sn2, Sn3 and Sn4) (Figure 52) and shows a
typical Sn4O2X2Y2-structural motif, (X, Y = OH, I), characteristic for tetraorganodistan-
noxanes.[23][48] This is due to OSn and ISn intramolecular coordinations. In analogy
to 27, the structure can formally be interpreted as containing a four-membered Sn2O2
ring that is coordinated by one CH2Sn(OH)ICH2SiMe3 moiety and one t-Bu2Sn(OH)I
(Scheme 24).
129
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Scheme 24. Formal interpretation of the solid-state structure of compound 28.
Si
Sn
Sn Sn
O
O
O
Me
Si
Sn
Sn
Sn
O
O
O
Me
I
Sn t-Bu
t-Bu
O
SiMe3
Me3Si
SiMe3
SiMe3Me3Si
SiMe3
  H2O
  t-Bu2SnI2(in solution)
(in solid state)
I
H
H
Si
Sn
Sn
Sn
O
O
O
Me
I
Sn t-Bu
t-Bu
O
SiMe3
SiMe3
SiMe3
I
H
H
130
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Both the endo-cyclic and exo-cyclic tin atoms exhibit a distorted trigonal bipyramidal
environments with the equatorial positions being occupied for the endocyclic Sn atoms
Sn2 and Sn3 by two carbon atoms and one oxygen atom (C(10), C(11), O(1) for Sn(2)),
(C(15), C(16), O(2) for Sn(3)). As to the axial positions, are being occupied for the endo-
cyclic tin atoms by two oxygen atoms (µ2–O(2), µ2–O(3) for Sn(2)), (µ2-O(1), µ2-O(4)
for Sn(3)). Also, for the exocyclic tin atom Sn(1) and Sn(4), respectively, the equatorial
positions are occupied by two carbon atoms and one oxygen atom (C(1), C(5), O(1) for
Sn(1)), (C(20), O(21), O(2) for Sn(4)), the axial position is occupied by two donor atoms
µ2–O(3) and I(1) for Sn(1) and µ2–O(4) and I(2) for Sn(4) (Figure 52). The geometrical
goodness[22] is ∆Σ(θ) =82.7◦ for Sn(1) , 82.6◦ for Sn(4), 95.0◦ for Sn(2), and 95.4◦ for
Sn(3). Notably, ∆Σ(θ) of Sn(2) and Sn(3) are higher than 90◦, this is probably due to the
distortion of the angles (C11–Sn2–C10) 142.53(14)◦, (C16-Sn3-C15) 143.21(14)◦, (C11–
Sn2–O2) 95.08(12)◦, and (C16-Sn2-O1) 99.04(12)◦ from the ideal geometry, respectively,
120 and 90◦. The Sn–O interatomic distances range between 2.033(2) and 2.196(3) Å. The
Snendo–µ2–OH–Snexo bridges are almost symmetric with Sn(1)–O(3) 2.175(3) Å, Sn(2)–
O(3) 2.195(3) Å, Sn(4)–O(4) 2.196(3) Å, and Sn(3)–O(4) 2.176(3) Å .
The Sn-I interatomic distances are 2.9173(4) Å for Sn(4)–I(2) and 2.9508(3) Å for Sn(1)–
I(1). As to the Snendo-µ2-O-Snendo bridges are comparable taking as example Sn(2)–
O(1) 2.048(2) Å and Sn(3) – O(1) 2.157(2) Å. This data is typical for such ladder-like
compounds.[20,22,23] Also the bond distances and angles around the silicon methylene-
bridged organotin arms C(9)–Si(1)–C(20), C(10)–Si(1)–C(20), C(15)–Si(1)–C(20), and
C(10)–Si(1)–C(15) are almost equal. The corresponding angles are, respectively, equal
to 109.8(17), 110.38(17), 108.19(16), and 114.06(16)◦. This refers to the tripod geometry
characteristic the novel organotin precursors.
The solid state structure of 28 is retained in solution. Thus, a 119Sn NMR spectrum of a
solution in CDCl3 of crystalline sample of 28 (Figure 54) shows four signal resonances
with equal ratio; 1:1:1:1. Two resonance signals at δ –183.5 and -183.2 ppm (2J(119Snexo-
117/119Snendo) = 248 Hz) refer to the exocyclic Sn(1) and Sn(4) atoms. The other two
resonance signals appear at -156 ppm (2J(119Snendo – 117Snendo) = 167 Hz) and -150
ppm (2J(119Snexo-117/119Snendo) = 242 Hz). These resonance shifts resemble to those
corresponding in [t-Bu2(µ2 – OH)Sn(µ3 – O)SnCl(CH2Si(Me)3)2].[23] These four signal
resonances correspond to four non-equivalent tin atoms, which matches perfectly with the
molecular structure found in solid state. This is the same case as the resembling compounds
presenting similar structural motifs [t-Bu2(µ2 – OH)Sn(µ3 – O)SnCl(CH2Si(Me)3)2],[23]
[t– Bu2(µ2 – OH)Sn(µ3 – O)SnPh(CH2(Me)2SiO)Sn – t– Bu2(µ3 – O)],[22] and
{[(R(Cl)Sn(CH2)3Sn(Cl)(CH2)2SiMe2]O2}2, R = CH2SiMe3.[20] The 29Si NMR
spectrum (see Supporting Information, Chapter 4, Figure S25) of this sample matches
also with the solid state structure of 28, there are three resonance signals at 0.72, 1.42,
131
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
and 1.58 ppm referring to the silicon atoms in the CH2SiMe3 groups bound to three
non-equivalent Sn atoms. The head SiMe resonance signal appears at -21 ppm. An
ESI-MS spectrum (positive mode, see Supporting Information Chapter 4, Figure S28-
30) of 28 shows one intense mass cluster centred at m/z 796.93 and one less intense
mass cluster at 750.93 corresponding, respectively, to the cations of [C16H43O3Si4Sn3]+ +
1
2 CH2Cl2: {[MeSi(CH2SnOCH2SiMe3)3] + H+ + 12 CH2Cl2}+ and [C16H43O3Si4Sn3]+:
{[MeSi(CH2SnOCH2SiMe3)3] + H+}+.These two mass clusters support the formation of
the adamantane-like structure [MeSi(CH2SnOCH2SiMe3)3 in solution, and, with caution,
the ring-opening mechanism for the formation path of 28, suggested in Scheme 24. Also
the 1H and 13C NMR spectra (CDCl3 solution, see Supporting Information, Chapter
4, Figure S24, S25) confirm as well the retention of the solid-state structure of 28 in
solution. Finally, in IR spectroscopy, we notice the presence of the absorption band at ν
3656-3493 cm−1 and ν 2950-2850 cm−1, corresponding to OH groups (See Supporting
Information, Chapter 4, Figure S32).
Figure 54. 119Sn NMR spectrum (149.26 MHz, CDCl3) of crystals sample of 28.
Treatment in CH2Cl2 of the organotin iodide 3 with (t-Bu2SnO)3 gave a reaction mixture
a 119Sn NMR spectrum of which displayed four resonances at δ 61 (t-Bu2SnI2), -203
(29), -225 (29), and -228 ppm (29), respectively (See Supporting Information, Chapter 4,
Figure S38). The spectrum indicates complete oxygen transfer from (t-Bu2SnO)3 to the
organotin iodide 5 and formation of t-Bu2SnI2 and the oktokaideka-nuclear (18-nuclear)
organotin oxide [MeSi(CH2SnPhO)3]6, 29 (Figure 55). The latter compound was isolated
from the reaction mixture as colourless crystalline material. It crystallized as a solvate
from dichloromethane solution. (Scheme 25)[45]
132
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Scheme 25. Synthesis of the macrocycle 29.
Si
Me
Sn
Sn
Sn
I
I
Ph
Ph
I
I
Ph
I
I
(t-Bu2SnO)3,CH2Cl2
  3 (t-Bu2SnI2)
[MeSi(CH2SnPhO)3]61/6
3
29
Figure 52 shows its molecular structure. The figure caption contains selected interatomic
distances and angles. Complete interatomic distances and angles are presented in Support-
ing Information, Chapter 4, Figure S54.[45]
133
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 55. Top: General view (ball and stick) of a molecule of the organotin oxide 29
containing the numbering of the atoms that appear below in the listing of distances and
angles. Only the Ci carbon atoms of the phenyl substituents, are shown. The hydrogen
atoms are omitted for clarity. Bottom: Side view of a molecule of 29 including the number-
ing for the silicon atoms. Selected interatomic distances (Å): Sn–C 2.05(2) (Sn6–C707)
– 2.256(17) (Sn16–C265), Sn–Oax 2.074(8) (Sn13–O13) – 2.158(7) (Sn4–O4), Sn–Oequ
2.009(9) (Sn7–O16) – 2.055(8) (Sn9–O18). Selected interatomic angles (◦): Cequ–Sn–Cequ
111.6(4) (C31–Sn3–C212) – 138.1(7) (C1–Sn15–C151), Oax–Sn–Oax 147.8(3) (O3–Sn4–
O4) – 150.8(3) (O17–Sn18–O18), Cax–Sn–Oax 150.0(4) (C262–Sn17–O7) – 153.4(4)
(C232–Sn8–O17).[45]
Compound 29 crystallizes in the monoclinic space group P21/n with four crystallographic
equivalent molecules in the unit cell. Each of these contains six MeSi(CH2SnPh)3 moieties
in which the tin atoms are connected by a total of 18 oxygen atoms giving a triangular
134
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
shaped, belt-like macromolecule with diameters ranging between 20.06(1) (H44· · ·H94)
and 23.00(1) (H84···H144) and a thickness ranging between 10.47(1) (H55· · ·H145) and
10.97(1) Å (H5· · ·H154) (Figure 56). Three MeSi moieties (containing Si1 – Si3) are
located above and three such moieties (containing Si4 – Si6) are located below the belt
formed by the 18 tin and 18 oxygen centres (Figure 56, Figure 57).[45]
Figure 56. Front view a) and side view b) (POV-Ray) of 29 including the H44· · ·H94
(20.06(1) Å) and H84· · ·H144 (23.00(1) Å) distances and the distances indicative for the
thickness (H55· · ·H155 10.47(1) Å, H5· · ·H154 10.97(1) Å).[45]
Figure 57. Simplified structure of 29 showing the non-equivalence of the SiCH3 moi-
eties.[45]
135
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Each of the 18 crystallographic independent tin atoms is penta-coordinated and shows
a distorted trigonal bipyramidal environment. For each of the Sn(1), Sn(3), Sn(4), Sn(6),
Sn(7), Sn(9), Sn(10), Sn(12), Sn(13), Sn(15), Sn(16), and Sn(18) atoms, the two carbon
atoms (Ci atom from the phenyl substituent and the methylene carbon atom) and one
oxygen atom occupy the equatorial positions. The corresponding Cequ–Sn–Cequ angles
vary between 111.6(4) (C31–Sn3–C212) and 138.1(7)◦ (C1–Sn15–C151). Two oxygen
atoms take the axial positions with the Oax–Sn–Oax angles varying between 147.8(3)◦
(O3–Sn4–O4) and 150.8(3)◦ (O17–Sn18–O18). The corresponding Sn–Oax distances vary
between 2.074(8) (Sn13–O13) and 2.158(7) Å (Sn4–O4). The Sn–Oequ distances involving
oxygen atoms in equatorial positions are slightly shorter and vary between 2.009(9) (Sn7–
O16) and 2.055(8) Å (Sn9–O18).
Notably, for the Sn(2), Sn(5), Sn(8), Sn(11), Sn(14), and Sn(17) atoms for each case the
corresponding methylene carbon atom and one out of the adjacent three oxygen atoms
take the axial positions whereas the Ci and the two remaining oxygen atoms occupy the
equatorial positions. This is in contrast to a situation as expected from the polarity rule
according to which the electronegative substituents occupy the axial positions in a trigonal
bipyramidal structure. The Cax–Sn–Oax angles vary between 150.0(4) (C262–Sn17–O7)
and 153.4(4)◦ (C232–Sn8–O17). The crystal packing of 29 (Figure 58) is characterized
by C–H· · ·pi interactions (Figure 59) at a H(144)-centroid (C171–C176) centroid distance
of 2.89(1) Å.[45]
Figure 58. Crystal packing of 29. The hydrogen atoms are omitted for clarity.[45]
136
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 59. Illustration of the C – H· · ·pi interactions at a H(144)-centroid (C171–C176)
centroid distance of 2.89(1) Å.[45]
The identity of compound 29 is retained in solution. The compound is kinetically in-
ert on the 1H, and 119Sn NMR time scales. Thus, a 1H NMR spectrum (CDCl3 so-
lution, Figures 60, 61) shows two resonances at δ 0.30 (integral 2) and 1.42 (inte-
gral 1) ppm, respectively, that are assigned to non-equivalent SiCH3 protons. The non-
equivalence of the SiCH3 protons (ratio 2:1) becomes visible when looking perpendic-
ular through the plane defined by the belt (Figure 57). The SiCH2 protons appear as
three equally intense AX-type resonances at δ 0.06 (2J(1H – 117/119Sn) 50 Hz, 2J(1H – 1H)
10 Hz)/0.48 (2J(1H – 117/119Sn) 70 Hz, 2J(1H – 1H) 10 Hz), 0.88 (2J(1H – 117/119Sn) 85 Hz,
2J(1H – 1H) 15 Hz)/1.20 (2J(1H – 117/119Sn) not measured, 2J(1H – 1H) 15 Hz), and 1.28
ppm (2J(1H – 117/119Sn) not measured, 2J(1H – 1H) 10 Hz)/1.91 (2J(1H – 117/119Sn) 120 Hz,
2J(1H – 1H) 10 Hz), respectively. 2D NMR spectra unambiguously support the assignment
of the 1H resonances (see Supporting Information Chapter 4, Figures S40- 43). A 119Sn
NMR spectrum of a solution of single crystalline 29 in CDCl3 shows three equally in-
tense resonances at δ 204 ppm (2J(119Sn – 117/119Sn) 180, 315 Hz; 2J(119Sn – 29Si) 59 Hz),
δ 225 ppm (2J(119Sn – 117/119Sn) 315 Hz), and δ 228 ppm (2J(119Sn – 117/119Sn) 180 Hz).
(See Supporting Information Chapter 4, Figures S39). The chemical shift is in agreement
with pentacoordinated tin atoms showing a SnC2O3 substituent pattern.[14,22,23] A 1H
137
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
DOSY NMR spectrum (CDCl3 solution, room temperature, Figure 62) provided a diffu-
sion coefficient of 3.9(1)×10−10 m2 s−1. This, by using the Einstein-Stokes equation, gave
a calculated hydrodynamic diameter of 20.8 Å and a sphere volume of 4813 Å3. These
values fit reasonably well with the single crystal X-ray diffraction data.[45]
Figure 60. 1H NMR spectrum (500.08 MHz, CDCl3) of compound 29.[45]
138
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 61. 1H NMR spectrum (500.08 MHz, CDCl3) of compound 29 (aliphatic part).[45]
Figure 62. 2D 1H DOSY NMR spectrum of [MeSi(CH2SnPhO)3]6, 29, in CDCl3.[45]
139
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Finally, an electrospray ionization mass spectrum (ESI MS; Supporting Information Chap-
ter 4, Figures S45- 52) revealed a mass cluster centred at m/z = 4324.1823 that corresponds
to {[MeSi(CH2SnPhO)3]6 + H+}, [29 + H]+. In addition, there are mass clusters centred
at m/z 1442.7312, m/z 2161.5910, 2884.4515, and m/z 3636.3600 that are assigned to
{[MeSi(CH2SnPhO)3]2 + H+}, {[MeSi(CH2SnPhO)3]3 + H+}, {[MeSi(CH2SnPhO)3]4 +
H+}, and {[MeSi(CH2SnPhO)3]5 + MeOH + H+}, respectively.
The reaction of the diorganotin diiodide derivative 11 with sodium hydroxide, NaOH, in
a mixture of dichloromethane, methanol, and water (Scheme 26) gave a crude reaction
mixture a 119Sn NMR spectrum of which was rather complex and showed both broad and
sharp resonances between 125 and 170 ppm (see Supporting Information, Figure S58).
After the work-up procedure, a microcrystalline material was obtained. From this, a crystal
was identified by single crystal X-ray diffraction analysis as the molecular diorganotin
oxide solvate 30. Figure 63 shows its simplified molecular structure and the figure caption
contains selected interatomic distances and angles. Complete interatomic distances and
angles are presented in Supporting Information Chapter 4, Figure S72.
The compound crystallizes in the triclinic space group P−1 with two molecules in the unit
cell.
Scheme 26. Synthesis of the macrocycle 30.
6 NaOH
CH2Cl2/ MeOH/ H2O
  6 NaI
[MeSi(CH2SnCH2SiMe3O)3]101/10
11
30
Si
Me
Sn
Sn
Sn
I
I
Me3SiH2C
Me3SiH2C
I
I
CH2SiMe3
I
I
Compound 30 is a trikonta-nuclear (30-nuclear) molecular diorganotin oxide
[MeSi(CH2SnRO)3]10 (R = Me3SiCH2) in which ten MeSi(CH2SnRO)3 moieties are con-
nected giving a belt-like ladder-type heart-shaped macrocycle (Figure 63). In this, the three
methyl groups attached to Si(14), Si(30), and Si(44), respectively, are above and the three
methyl groups attached to Si(17), Si(32), and Si(43), respectively, are below the ring plane.
The two methyl groups attached to Si(22) and Si(26), respectively, point into the ring cav-
ity and the two methyl groups attached to Si(10) and Si(38), respectively, point outside
the ring (Figure 64, left). The methylene carbon atoms C(111), C(121), C(371), C(391),
C(401), and C(491) which are attached to Sn(1), Sn(30), Sn(11), Sn(10), Sn(9), and Sn(2),
respectively and which belong to the trimethylsilylmethyl substituents point also inside the
ring while the remaining substituents point outside (Figure 64, right). The overall structure
140
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
is rather complex. A closer inspection reveals it formally being composed of different sub-
units, i. e., the corner units a (with Sn3–Sn8), b (with Sn24–Sn29), and c (with Sn12–Sn17),
the double spacer d (with Sn18–Sn23), and the single spacers e (with Sn1, Sn2, Sn30) and
f (with Sn9–Sn11) (Figure 63). Like in the oktokaideka-nuclear diorganotin oxide 29, all
tin centres in 30 are five-coordinated and, except Sn(1), show distorted trigonal bipyrami-
dal environments. For the Sn(2)–Sn(4), Sn(7)–Sn(13), Sn(16)–Sn(25), Sn(29), and Sn(30)
atoms, for each case two carbon atoms (the Me3SiCH2 and the MeSiCH2 methylene carbon
atoms) and one oxygen atom occupy the equatorial positions. The other two oxygen atoms
take the axial positions. The corresponding Ceq–Sn–Ceq angles vary between 119.0(10)
(C311–Sn16–C321) and 139.8(15)◦ (C151-Sn28-C173). The Oax–Sn–Oax angles vary be-
tween 145.2(9) (O1–Sn2–O3) and 153.8(7)◦ (O10-Sn11-O12). The Sn(1) atom exhibits a
distorted square pyramidal environment with the O(2), O(30), C(101), and C(111) atoms
occupying the equatorial positions with O(2)–Sn(1)–O(30) and C(101)–Sn(1)–C(111) an-
gles of 150.5(8) and 154(2)◦, respectively. The O(1) atom occupies the apical position.
The geometry about the Sn(28) atom is a borderline case between trigonal bipyramidal
and square pyramidal with the O(27)–Sn(28)–O(29) and C(151)–Sn(28)–C(173) angles
being 149.7(8) and 139.8(15)◦. In analogy to 29, there are again six tin centres (Sn5,
Sn6, Sn26, Sn27, Sn14, Sn15) belonging to the corner units (a), (b), and (c), respectively,
that violate in their coordination environment the polarity rule.[52] For each of these tin
centres, the corresponding MeSiCH2 methylene carbon atom and one out of the adjacent
three oxygen atoms take the axial positions whereas the Me3SiCH2 methylene carbon
and the two remaining oxygen atoms occupy the equatorial positions. The Cax-Sn–Oax
angles vary between 146.2(11) (O6–Sn6–C432, in a) and 150.9(10)◦ (O14–Sn14–C322,
in c). Figure 65 shows with diameters ranging between H24F· · ·H46F (27.51(1) Å) and
H16K· · ·H34K (33.98(1) Å) and a thickness ranging between H34D· · ·H35D 9.71(1) Å
and H11F· · ·H49C 11.96(1) Å. Figure 66 shows the packing of 30 in the crystal. The
Sn30O30 belt is located in the (2, -2, 0) plane.[45]
141
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 63. Top: General view (ball and stick) of a molecule of the organotin oxide 30
containing the numbering of the atoms that appear below in the listing of distances and
angles. The hydrogen atoms are omitted for clarity. Bottom: Side view of a molecule of
30 including the numbering for the silicon atoms. The labels a–f refer to the different
building blocks the belt-type structure is composed of. Selected interatomic distances (Å).
Sn–O: 1.95(2) (Sn25–O25, in b) - 2.23(2) (Sn8–O7, in a), Sn–C: 2.01(8) (Sn1–C111, in e)
– 2.38(4) (Sn28–C151, in b). Selected interatomic angles (◦). Oax–Sn–Oax: 145.2(9) (O1–
Sn2–O3, in e) – 153.8(7) (O10–Sn11–O12, in f), Ceq–Sn–Ceq: 119.0(10) (C311–Sn16–
C321, in c) - 139.8(15) (C151–Sn28–C173, in b), Cax–Sn–Oax: 146.2(11) (O6–Sn6–C432,
in a) - 150.9(10) (O14–Sn14–C322, in c).[45]
142
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 64. Simplified molecular structure of 30 illustrating the positions of the SiCH3
moieties and the substituents at the tin atoms pointing inside the cavity.[45]
Figure 65. Front view a) and side view b) (POV-Ray) of 30 including the H24F· · ·H46F
(27.51(1) Å) and H16K· · ·H34K (33.98(1) Å) distances and the distances indicative for
the thickness (H34D· · ·H35D 9.71(1) Å, H11F· · ·H49C 11.96(1) Å).[45]
143
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 66. Crystal structure of 30. The hydrogen atoms are omitted for clarity.[45]
Although the elemental analysis of the bulk crystalline material, obtained from the reac-
tion between 11 and NaOH (Scheme 26), perfectly matches with the empirical formula
[MeSi(CH2SnCH2SiMe3O)3]n, one cannot be sure whether it exclusively consists of the
trikonta-nuclear species 30 (n = 10). Given the insufficient amount of material, no powder
X-ray diffraction analysis of the bulk material was performed.[45]
A 119Sn NMR spectrum of a CDCl3 solution of the crystalline bulk material the sin-
gle crystal was taken from, (Supporting Information Chapter 4, Figure S59) in CDCl3
revealed three, within the experimental error almost equally intense, resonances at δ –
148 (2J(119Sn – 117/119Sn) = 230 Hz), δ –159 (2J(119Sn – 117/119Sn) = 257 Hz), and δ –164
ppm (2J(119Sn – 117/119Sn) = 219 Hz). In addition, there are hub-like, partially structured
broad resonances between δ –126 and δ –146 ppm. A 29Si NMR spectrum (Supporting
Information Chapter 4, Figure S57) of the same sample showed a major intense broad
unsymmetrically shaped signal at δ 0.9 ppm and a sharp resonance at δ –21.9 ppm. A
1H NMR spectrum (Supporting Information Chapter 4, Figure S55) revealed signals for
the SiCH3, SiCH2Sn, SnCH2SiMe3, and Si(CH3)3 protons with correct integral ratio of
3:6:6:27. Attempts at obtaining 1H DOSY NMR spectrum failed as the sample became
gel-like over time. From the NMR data at hand, we conclude that the identity of 30 is
not retained in solution. Apparently, the solution contains a mixture of different species.
144
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
With caution and in analogy to 29, we assign the three sharp 119Sn resonances (vide supra)
to the oktokaideka-nuclear diorganotin oxide [MeSi(CH2SnCH2SiMe3O)3]6. Either, the
latter is present right from the beginning in the isolated bulk crystalline material or it forms
upon dissolution of this material.[45]
An ESI MS (Supporting Information Chapter 4, Figure S61- 70) of a so-
lution of the microcrystalline bulk material in CH3CN/CH2Cl2 revealed
mass clusters centred at m/z 750.9293, 768.8946, 788.9056, 1646.8168,
1669.6017, 2254.7523, 3077.6608, and 4506.3980. These are assigned to
[MeSi(CH2SnCH2SiMe3O)3 + H+]+, [MeSi(CH2SnCH2SiMe3O)3 + H2O +
H+]+, [MeSi(CH2SnCH2SiMe3O)3 + K+]+, {[MeSi(CH2Sn(OH)2CH2SiMe3)3]2 +
2H2O + H+}+, {[MeSi(CH2Sn(OH)2CH2SiMe3)3]2 + CH3CN + H2O + H+}+.
{[MeSi(CH2SnCH2SiMe3O)3]6 + 2H+}2+, {[MeSi(CH2SnCH2SiMe3O)3]4 + H+}+,
and {[MeSi(CH2SnCH2SiMe3O)3]6 + H+}+, respectively.[45]
Although no detailed mechanistic studies have been performed, the formation of 29 and
30 can formally be seen as a stepwise process as shown in Scheme 27. Molecular diorgan-
otin oxides A with adamantane-type structure undergo ring-opening dimerization via the
intermediate B giving the hexanuclear product C. In case of R = Ph, three C-moieties
assemble giving the oktokaideka-nuclear diorganotin oxide 29. In case of R = Me3SiCH2,
however, C-moieties combine with A- and B-type moieties giving, as one product out
of probably several, the trikonta-nuclear molecular diorganotin oxide 30. This view gets
support from the ESI mass spectrometric studies revealing mass clusters that are in line
with the presence of A- and C-type moieties (vide supra).[45]
145
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Scheme 27. Association of two adamantane-type diorganotin oxide moieties A undergoing
subsequent ring-opening dimerization giving C. The existence in solution of these moieties
gets support from electrospray ionization mass spectrometry.[45]
Finally, attempts failed at obtaining host-guest complexes by recrystallizing compound 7
in the presence of elemental sulphur, CCl4, C2Cl4, and PPh4I, respectively. This statement
is in coherence with the fact that compounds 29 and 30 present tiny “cavities” with volume
of about 8 Å3, which is even too small to host a water molecule.[45]
A 119Sn NMR spectrum of the crude mixture (Figure 67) in CDCl3 obtained from
the reaction between the organotin iodide 3 and (t-Bu2SnO)3 shows signal resonances
referring to compound 29 at δ –204 , -225 , and -228 ppm with a total integral of
67 %, the by-product t-Bu2SnI2 at δ 63, and four further equally intense resonances
at δ –233, -230, -196, and -173 ppm, with an integration of 20 %, referring to a Sn-
containing unknown product. From this reaction mixture a crystalline material of
[(MeSi(CH2)3)Sn(µ3-O)3(Ph)Sn(I)(Ph)Sn(µ2-OH)(Ph)Sn(t– Bu)2]2, 31, was isolated suit-
able for X-ray diffraction study.
146
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 67. 119Sn NMR spectrum of the crude mixture (149.26 MHz, CDCl3) giving com-
pound 29 and 31.
The molecular structure of 31 is shown at Figure 68, selected interatomic distances and
angles are listed in the figure caption. It crystallizes in the monoclinic space group P21/n
as 31·5 DMF solvate. It shows an octanucluear ladder-like dimeric structure resembling
to Compound 26 with iodine instead of chlorine substituents in the skeleton. Compound
31 is presenting a middle-stage of formation of the 18-Sn containing oxo-cluster 29. We
can consider it formed from a one-third moiety of 29 composed of [MeSi(CH2SnOPh)3]2
with coordination with two t-Bu2SnIOH molecules (Figure 69); these latter are resulted
from reaction of two t-Bu2SnI2 and two H2O molecules.
This structure is like that of 26, composed of four 6-membred-rings
(Si – C – Sn – O – Sn – C) and seven 4-membred Sn2O2-rings. (Figure 68).
147
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 68. POV-Ray image presented in balls and sticks of the molecular structure
of [(MeSi(CH2)3)Sn(µ3-O)3(Ph)Sn(I)(Ph)Sn(µ2-OH)(Ph)Sn(t-Bu)2]2, 31. Only Ci of the
phenyl groups are shown for clarity. The DMF solvate molecules are omitted for
clarity. Selected interatomic distances (Å): Sn(2)–O(3) 2.094(8), Sn(3)–O(2) 2.183(8),
Sn(5)–O(6) 2.073(8), Sn(6)–O(5) 2.155(8), Sn(7)–O(6) 2.098(8), Sn(1)–O(1) 2.187(8),
Sn(4)–O(3) 2.064(8), Sn(1)–I(1) 2.9020(14), and Sn(8)–I(2) 2.9395(13), O(1)–H(1) 0.868
, O(8)–H(8) 0.865. Selected interatomic angles (◦): O(1)–Sn(1)–O(2) 73.0(3), O(1)–
Sn(2)–O(3) 149.0(3), O(2)–Sn(3)–O(3) 72.8(3), O(4)–Sn(3)–O(2) 146.3(3), C(41)–Sn(4)–
O(3) 115.7(4), O(4)–Sn(4)–C(212) 154.0(4), O(5)–Sn(5)–C(312) 151.5(4), O(6)–Sn(5)–
O(5) 72.5(3), O(5)–Sn(6)–O(6) 73.3(3), C(71)–Sn(7)–O(6) 95.7(4), O(7)–Sn(8)–C(821)
117.5(4), O(1)–Sn(1)–I(1) 160.8(2), O(8)–Sn(8)–I(2) 157.72(19), Si(21)–C(212)–Sn(4)
111.1(5), and Si(21)–C(213)–Sn(6) 121.7(6).
148
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 69. Presentation of 31 as one-third moiety of 29; [MeSi(CH2SnOPh)3]2 with coor-
dination with two t-Bu2SnIOH molecules.
The endo-cyclic- (Sn2, Sn3, Sn4, Sn5, Sn6, and Sn7) and exo-cyclic- (Sn1 and Sn8) tin
atoms exhibit distorted trigonal bipyramidal environments.
For each of the Sn(2), Sn(3), Sn(6), and Sn(7) atoms, the two carbon atoms (Ci atom from
the phenyl substituent and the methylene carbon atom) and one oxygen atom occupy the
equatorial positions. The corresponding Cequ-Sn-Cequ angles vary between 119.0(5)◦ (C21–
Sn2–C211) and 132.8(4)◦ (C31–Sn3–C311). Two oxygen atoms take the axial positions
with the Oax–Sn–Oax angles varying between 145.5(3) (O5–Sn6–O7) and 149.0(3)◦ (O1–
Sn2–O3). As for the exo-cyclic Sn(1) and Sn(8) atoms, the two carbon atoms (C atoms
from the two t-Bu substituents) and one oxygen atom occupy the equatorial positions.
The corresponding Cequ–Sn–Cequ angles are almost equal with values of 125.9(5)◦ (C111–
Sn1–C121) and 126.8(5)◦ (C812–Sn8–C821). One oxygen and one iodine atom take the
axial positions with the Oax–Sn–Iax angles varying between 157.72(19)◦ (O8–Sn8–I2) and
160.8(2)◦ (O1–Sn1–I1).
The corresponding Sn–Oax distances vary between 2.031(8) (Sn4–O5) and 2.183(8) Å
(Sn3–O2). The Sn-I distances are 2.9020(14) (Sn1-I1) and 2.9395(13) Å (Sn8–I2). The
149
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Sn–Oequ distances involving oxygen atoms in equatorial positions are slightly shorter and
vary between 2.018(8) (Sn6–O6) and 2.073(8) Å (Sn5–O6).
Notably, like for the tinoxo-cluster 29, for the tin atoms Sn(4) and Sn(5) for each case the
corresponding methylene carbon atom and one out of the adjacent three oxygen atoms
take the axial positions whereas the Ci and the two remaining oxygen atoms occupy the
equatorial positions. This is in contrast to a situation as expected from the polarity rule
according to which the electronegative substituents occupy the axial positions in a trigonal
bipyramidal structure. The Cax–Sn–Oax angles vary between 151.5(4)◦ (O5–Sn5–C312)
and 154.0(4)◦ (O4–Sn4–C212). The geometrical goodness[22] ∆Σ(θ) is 76.7◦ for Sn(1),
89.7◦ for Sn(2), 95.3◦ for Sn(3), 56◦ for Sn(4), 54.4◦ for Sn(5), 85.2◦ for Sn(6) , 90.2◦ for
Sn(7), and 80.2◦ for Sn(8). Notably, ∆Σ(θ) of Sn(3) is higher than 90◦, this is probably
due to the distortion of the angles (C31–Sn3–C311) 132.8(4)◦ from the ideal geometry of
120◦.
Angles around the silicon methylene-bridged organotin arms are almost equal, varying
between 111.1(5)◦ (Si21–C212–Sn4) and 121.7(6)◦ (Si21–C213–Sn6). As the matter of
fact, we observe in Compound 31, same the case for 26 the Sn4O2X2Y2-structural motif,
(X, Y = OH, I), characteristic for di-organostannoxanes.[23,47,48] This motif is presented
as Sn4O6OH2I2, exhibiting an asymmetric combination, in which the hydroxyl groups are
located in the bridging positions and the iodine atoms are bonded to the exo-cyclic tin
atoms.
Given the lack of sufficient amount of material, no further investigations in solution could
be realized. However, the 119Sn NMR resonance shifts of 31 (Figure 67) resembles the
corresponding signals observed for 26 at δ –230, -228, -209, and -196 ppm. They are all
equally intense, which matches with the solid state structure of 31. We can with caution
presume that the solid state structure is also retained in solution like the case for compound
26.
An attempt of recrystallization the nonabromido-organotin compound 9 under non-inert
condition from dichloromethane/ethanol solution gives a product of partial hydrolysis as
brownish needles suitable for X-ray diffraction study (Scheme 28). The compound 32
crystallized as its ethanol solvate [MeSi(CH2SnBr)3(µ2-OH)2(µ4-O)(µ3-OEt)2]2 ·2EtOH.
It is almost insoluble in all organic solvents.
150
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Scheme 28. Synthesis of the hexanuclear organotin oxo-cluster ladder-like compound 32.
Si
Me
Sn
Sn
Sn
Br
Br
Br
Br
Br
Br
Br
Br
Br
12 EtOH
CH2Cl2
9
Si Me
Sn
Sn
Si
Me
Sn
Sn
SnSn
O O
O
O
O
Br
O BrO
Br
Br
H
BrO
O
O H
Br
H
H
OHEt
OHEt
+ 6 C2H4Br2
32
6 H2O+
Figure 70. Different perspectives of the three ladder-like structures connected via nine
Sn2O2 rings in the skeleton of 32.
151
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 71. POV-Ray image of the molecular structure of
[MeSi(CH2SnBr)3(µ2-OH)2(µ4-O)(µ3-OEt)2]2 ·2EtOH, 32. The protons of the sol-
vate groups between O(1L) and O(2A), and O(1LA) and O(2) cannot be found on the
electron density map. Only one solvate group is shown. Selected interatomic distances (Å):
Sn(1)–Br(1) 2.5555(13), Sn(1)–Br(2) 2.6610(12), Sn(1)–O(3A) 2.177(6), Sn(1)–O(4A)
2.158(7), Sn(1)–O(5) 2.147(6), Sn(2)–O(1) 2.097(7), Sn(2)–O(2) 2.068(7), Sn(2)–O(3A)
2.332(6), Sn(3)–O(5) 2.113(6), Sn(3)–O(1) 2.140(6), Sn(3)–O(3A) 2.144(6), Sn(3)–O(3)
2.097(6), Sn(3)–O(2A) 2.098(7), Sn(3)–O(4) 2.107(6), O(1)H(1)· · ·Br(2A) 1.747,
and O(2)–H(2)· · ·O(1LA) 2.378. Selected interatomic angles (◦):C(1)–Sn(1)–O(4A)
164.0(3), O(5)–Sn(1)–O(3A) 77.8(2), Br(1)–Sn(1)–O(3A) 162.41(17), Br(2)–Sn(1)–
O(5) 169.23(18), Br(1)–Sn(1)– Br(2) 91.83(4), C(2)–Sn(2)–O(2) 167.2(3), O(1)–
Sn(2)–O(5) 150.0(2), Br(3)–Sn(1)–O(5) 104.15(17), Br(3)–Sn(1)–O(3A) 159.88(16),
O(1)–Sn(1)–Br(3) 105.33(18), C(3)–Sn(3)–O(3) 168.9(3), O(1)–Sn(3)–O(4) 83.6(2),
O(3A)–Sn(3)–O(4) 147.0(3), O(1)–Sn(3)–O(2A) 164.7(3), and O(2A)–Sn(1)–O(3A)
97.2(2).
152
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 71 shows the molecular structure of compound 32. The figure caption contains
selected interatomic distances and angles. Compound 32 crystallizes in the monoclinic
space group P21/n. It shows a centro-symmetric hexanuclear organotin oxo-cluster, pre-
sented as a dimer in the solid state, via bridging Sn–Br and Sn–O intramolecular interac-
tions. There are three ladder-like structures connected with each other via nine Sn2O2
rings (Figure 70). Figure 70 shows the molecular structure of 32 from different per-
spectives. This dimer is formed via two (µ4–O); O(3) and O(3A), two hydrogen bonds
(µ2–OH· · ·Br); O(1)H(1)· · ·Br(2A) and O(1A)H(1A)· · ·Br(2), two hydrogen bonds via
coordination with the solvent molecules (µ2–O–H· · ·OEt); O(2)–H(2)· · ·O(1LA)Et, and
O(2A)–H(2A)· · ·O(1L)Et and four ethoxy- substituents; O(4)Et, O(4A)Et, O(5)Et and
O(5A)Et.
All six tin centres are hexa-coordinated, and exhibit each a distorted octahedral all-trans
environment, with three different types of coordinations on each two symmetrical Sn
centres. For Sn(1) and Sn(1A), there is a SnCBr2O3 environment with angles of (C1–Sn1–
O4A) 164.0(3)◦, (O5–Sn1–O3A) 77.8(2)◦, (Br1–Sn1–O3A) 162.41(17)◦, (Br2–Sn1–O5)
169.23(18)◦, and (Br1–Sn1–Br2) 91.83(4)◦. For Sn(2) and Sn(2A), there is a SnCBrO4
environment with angles of (C2–Sn2–O2) 167.2(3)◦, (O1–Sn2–O5) 150.0(2)◦, (Br3–Sn1–
O5) 104.15(17)◦, (Br3–Sn1–O3A) 159.88(16)◦, and (O1-Sn1- Br3) 105.33(18)◦. For Sn(3)
and Sn(3A), there is a SnCO5 environment with angles of (C3–Sn3–O3) 168.9(3)◦, (O1–
Sn3–O4) 83.6(2)◦, (O3A–Sn3–O4) 147.0(3)◦, (O1–Sn3–O2A) 164.7(3)◦, and (O2A–Sn1–
O3A) 97.2(2)◦.
There is an overall symmetry characterising this structure. The Br-Sn-Br bridge is ap-
proximately symmetric with Sn(1)–Br(1) and Sn(1)–Br(2) distances of 2.5555(13) and
2.6610(12) Å, respectively. Sn2–Br3 is also nearly equal with distance of 2.5255(12) Å.
The O–Sn–O bridges are almost symmetric with distances for Sn1 of Sn(1)–O(3A), Sn(1)–
O(4A), and Sn(1)–O(5), respectively, equal to 2.177(6), 2.158(7), and 2.147(6) Å. For
Sn(2) the distances of Sn(2)–O(1), Sn(2) – O(2), Sn(2)–O(3A), and Sn(3)–O(5) are equal
to 2.097(7), 2.068(7), 2.332(6), and 2.113(6) Å, respectively. For Sn(3), the distances
of Sn(3) – O(1), Sn(3)–O(3A), Sn(3)–O(3), Sn(3)–O(2A), and Sn(3)–O(4), are equal to
2.140(6), 2.144(6), 2.097(6), 2.098(7), and 2.107(6) Å, respectively.
The hydrogen bonds O(1)H(1)· · ·Br(2A) and O(2)–H(2)· · ·O(1LA)Et are equal to 1.747
and 2.378 Å, respectively.
This reaction is reproducible. The study of 32 in solution is not realizable, given the
insolubility of this compound in almost all organic solvents. However an ESI-MS spectrum
of this crystalline material (negative mode, see Supporting Information, Chapter 4, Figures
S73, 74) shows one mass cluster with minor intensity centred at m/z 1610.3 corresponding,
respectively, to the anions of [C20H57Br4O14Si2Sn6] −: [M – Br2 + OH– + H2O]– . In IR
spectroscopy, we notice the presence of the absorption band at ν 3501-3318 cm−1 and ν
153
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
2969-2893 cm−1, corresponding to OH groups (See Supporting Information, Chapter 4,
Figure S75).
4.3 Novel S-, Se- containing silastannaadamantanes: syn-
theses, structures, and redistribution reactions
The 119Sn NMR spectrum in CDCl3 of a white residue, obtained from a reaction be-
tween one molar equiv of the diorganotin diiodide derivative 3 and 3.2 molar equiv of
Na2S in acetone/methanol/water solution (Scheme 30) shows one singlet resonance at
98 ppm with a coupling constant 2J(119Sn – 117Sn) = 187 Hz (Figure 72). A crystalline
material of 7-Methyl-1,3,5-tris(triphenyl-2,4,9-trithio-7-sila-1,3,5-tristannaadamantane,
MeSi(CH2SnPhS)3, 33, was isolated from a diethyl-ether/dichloromethane solution as
transparent needles suitable for X-ray diffraction study. Compound 33 is soluble in both
polar and non-polar organic solvents.
Figure 72. 119Sn NMR spectrum (223.85 MHz, CDCl3) of the crude mixture of the reac-
tion of formation of of 33.
154
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Scheme 29. Synthesis of the silastannaadamantane compound 33.
Si
Sn
Sn
Sn
Ph
Ph S
S
S
Me
Ph
Si
Me
Sn
Sn
Sn
I
I
Ph
Ph
I
I
Ph
I
I
3 Na2S, 
acetone/ MeOH/ H2O
− 6 NaI
3 33
Figure 73. Left: POV-Ray image of the molecular structure of MeSi(CH2SnPhS)3, 33.
Protons are omitted for clarity. Right: Overall symmetry of 33. Selected interatomic dis-
tances (Å): Sn1–S1 2.4097(12), Sn1A–S1 2.4162(12), Si(1)–C(2) 1.870(5), Sn(1)–C(2)
2.131(5). Selected interatomic angles (◦): C(2)–Sn(1)–S(1) 107.44(13), C(11)–Sn(1)–
S(1) 103.30(12), S(1A)–Sn(1)–S(1) 109.37(6), C(2)–Sn(1)–C(11) 119.84(18), C(2)–Sn(1)–
S(1A) 111.91(13), C(11)–Sn(1)–S(1A) 104.40(13), Sn(1A)–S(1)–Sn(1) 99.16(5), S(1)–
Sn(1A)–(S1A) 109.37(6), Si(1)–C(2)–Sn(1) 117.8(2).
Figure 73 shows the molecular structure of compound 33 and the figure caption contains
selected interatomic distances and angles. Compound 33 crystallizes in the trigonal space
group R3C. It shows an almost perfectly symmetric adamantane structure composed of
155
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
three six-membred rings (Si – C – Sn – S – Sn – C). It represents the first adamantane con-
taining carbon, silicon and tin atoms in the skeleton.[10,50,53]
The environments about the tin atoms are distorted tetrahedral, with angles of
C(2) – Sn(1) – S(1), C(2) – Sn(1) – S(1), S(1A) – Sn(1) – S(1), S(1A) – Sn(1) – S(1),
S(1A) – Sn(1) – S(1), S(1A) – Sn(1) – S(1), respectively, equal to 107.44(13), 103.30(12),
109.37(6), 119.84(18), 111.91(13), and 104.40(13)◦. The distortions from the ideal
tetrahedral geometry are not significant.
This adamantane structure consists of three bridging S atoms in which all Sn – S – Sn
angles are equal to (Sn1A–S1–Sn1) 99.16(5)◦. This angle is similar to that corresponding
in [(PhSSn)2(CH2)3]2 (Sn1-S1-Sn2) (99.62(4)◦)[53] and smaller than those corresponding
in [(PhSSn)2CH2]2, varying between 102.2(1) and 104.0(1)◦.[10] As well, all S-Sn-S angles
are equal to 109.37(6)◦, these latter are similar to those in [(PhSSn)2(CH2)3]2 (S1–Sn1–
S2) (108.26(4)◦) and (S1–Sn2–S2) (109.47(4)◦) and in [(PhSSn)2CH2]2 (S1–Sn2–S3)
(109.4(4)◦)[10] and larger than those reported for [PhSn(S2CNEt2)]2(S)(CH2)3 (S1–Sn1–
S2) (95.54(5)◦) and (S2–Sn1–S3) (65.41(5)◦).[53]
The overall symmetrical characteristic of the molecular structure of 33 is also proved by the
evenness of the angles at the silicon methylene-bridged organotin arms, which are all equal
to (Si1–C2–Sn1) 117.8(2)◦. This statement refers to the tripod geometry characteristic of
these novel organotin precursors. The Sn–S bond distances are symmetrical and equal
to 2.4097(12) Å (Sn1–S1) and 2.4162(12) Å (Sn1A–S1), these bond distances are very
similar to those corresponding in [(PhSSn)2(CH2)3]2 varying between (Sn1–S2) 2.397(1)
Å and (Sn1–S1) 2.407(1) Å ,[53] and [(PhSSn)2CH2]2 varying between (Sn1–S2) 2.388(2)
Å and (Sn1–S1) 2.425(1) Å .[10] Also the Si-C-Sn bridges are all similar with distances of
1.870(5) and 2.131(5) Å, respectively corresponding to Si(1)–C(2) and Sn(1)–C(2).
The identity of compound 33 is retained in solution. The compound is kinetically inert on
the 1H, 13C, 29Si and 119Sn NMR time scales. Thus, a 1H NMR spectrum (CDCl3 solution,
see Supporting Information, Chapter 4, Figure S77) shows the resonance signal of SiCH3
protons appearing at δ 0.43 ppm (4J(1H – 117/119Sn) = 11 Hz). The SiCH2 protons, with
integration of 6H, appear at δ 0.80 ppm (2J(1H – 117/119Sn) = 72 Hz). The complex pattern
referring to the protons of the phenyl groups appears at δ 7.42-7.77 ppm with integration
of 15H. In a 13C NMR spectrum (CDCl3 solution, see Supporting Information, Chapter 4,
Figure S78), the resonances corresponding to the SiCH2Sn carbon atoms appear at δ 5.41
ppm (1J(13C – 29Si) = 47 Hz, 1J(13C – 117/119Sn) = 279/292 Hz), and those of SiCH3 at δ
8.4 ppm (3J(13C – 117/119Sn) = 44 Hz, 1J(13C – 29Si) = 85 Hz). In the aromatic part, the Cm
resonance appears at δ 128.9 ppm (3J(13C – 117/119Sn) = 70 Hz), the Cp at δ 130.1 ppm
(4J(13C – 117/119Sn) = 10 Hz), the Co at δ 134.4 ppm (2J(13C – 117/119Sn) = 57 Hz), and
the Ci at δ 141.4 ppm (1J(13C – 117/119Sn) = 615/645 Hz). A 29Si NMR spectrum (CDCl3
solution, see Supporting Information Chapter 4, Figure S79) shows a resonance referring
to the MeSi silicon atom at δ 13.4 ppm (2J(29Si – 117/119Sn) = 50 Hz, 1J(29Si – 13C) =
156
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
94 Hz). The 119Sn NMR spectrum of a crystalline material of 33 in CDCl3 (Figure 74)
shows a resonance at δ 98 ppm (2J(119Sn – 117Sn) = 190 Hz) referring to three equivalent
tin atoms which matches perfectly with the molecular structure found for the solid state.
This signal is similar to that reported for the stannaadamantane [(PhSSn)2CH2]2 at δ 106
ppm (2J(119Sn – 117Sn) = 195 Hz),[10] and high-frequency-shifted comparing to the corre-
sponding Sn atoms in [(PhSSn)2(CH2)3]2 at δ 53 ppm (2J(119Sn – 117Sn) = 183 Hz).[53]
An ESI-MS spectrum (positive mode) of 33 shows one mass cluster centred at m/z 793.0
corresponding to the cation [C22H24NaS3SiSn3]+ ([M + Na+]+), which confirms that the
cluster remains intact in solution even under harsh ESI-MS conditions (See Supporting
Information, Chapter 4, Figures S82, S83).
Figure 74. 119Sn NMR spectrum (149.26 MHz, CDCl3) of compound 33.
We wanted to investigate the stability of 33 in solution, and the possibility to form further
structural isomers in solution, which is known for such stannadamantane compounds.[50]
Upon addition of one molar equiv of F– as NEt4F2 ·2H2O to one molar equiv of 33 in
CDCl3, the 119Sn NMR spectrum shows the same resonance as the silastannaadamantane
33 (see supporting Information, Chapter 4, Figure S85), which is opposite to the affirmation
saying that of addition of Lewis base may catalyze the formation of other structural isomers
in solution.[53] To study the possibility of exchange reaction between a structurally alike
organotin oxide compound 29, [MeSi(CH2SnPhO)3]6 and the silastannaadamantane 33,
157
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
MeSi(CH2SnPhS)3. Upon addition of one molar equiv of 29 to six molar equiv of 33 in
C6D6, the 119Sn NMR spectrum shows the three resonances referring to 29 at δ –228,
-225, and -204 ppm and the signal referring to 33 at δ 98 ppm (See supporting Information,
Chapter 4, Figure S86).
The 119Sn NMR spectrum in CDCl3 of a white residue, obtained from a reaction of one mo-
lar equiv of the dichlorido-derivative 4 with 3.2 molar equiv of Na2Se in acetone/methanol-
water solution shows one singlet resonance at 3.7 ppm with coupling constants
2J(119Sn – 117Sn) = 220 Hz and 1J(119Sn – 77Se) = 1221 Hz (Figure 75). From a solution of
dichloromethane/diethylether, a crystalline material was isolated from this reaction mix-
ture as transparent needles suitable for X-ray diffraction study. It proved to be 7-Methyl-
1,3,5-tris(triphenyl-2,4,9-triselena-7-sila-1,3,5-tristannaadamantane MeSi(CH2SnPhSe)3,
34 (Scheme 30). Compound 34 shows very good solubility in organic solvents.
Figure 75. 119Sn NMR spectrum (223.85 MHz, CDCl3) of the crude mixture of the reac-
tion of formation of 34.
158
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Scheme 30. Synthesis of the Se-silastannaadamantane compound 34.
Si
Sn
Sn
Sn
Ph
Ph Se
Se
Se
Me
Ph
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
3 Na2Se, 
acetone/ MeOH/ H2O
− 6 NaCl
4 34
Figure 76 shows the molecular structure of compound 34. The figure caption contains
selected interatomic distances and angles. Compound 34 crystallizes in the monoclinic
space group P21/c. It shows an almost symmetrical adamantane structure. The structure
of 34 is similar to a first approximation to that of 33. Figure 76 (right) shows the overall
symmetry characteristic of the new Se-containing silastannaadamantane structure 34.
159
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 76. Left: POV-Ray image of the molecular structure of MeSi(CH2SnPhSe)3, 34.
Right: Overall symmetry characteristic of 34. Protons are omitted for clarity. Selected
interatomic distances (Å): Si(1)–C(1) 1.858(3), Si(1)–C(2) 1.870(3), Si(1)–C(3) 1.868(3),
Sn(1)–C(1) 2.124(3), Sn(1)–C(2) 2.134(3), Sn(1)–C(3)2.135(3), Sn(1)–Se(1) 2.5354(3),
Sn(1)–Se(2) 2.5353(3), Sn(2)–Se(2) 2.5208(3), Sn(2)–Se(3) 2.5473(3), Sn(3)–Se(1)
2.5323(3), Sn(3)–Se(2) 2.5209(3). Selected interatomic angles (◦): C(11)–Sn(1)–Se(1)
105.24(7), Se(2)–Sn(1)–Se(1) 111.868(11), C(21)–Sn(2)–Se(3) 102.61(7), C(21)–Sn(2)–
C(2) 114.66(10), C(31)–Sn(3)–Se(3) 106.65(7), Se(3)–Sn(3)–Se(1) 112.718(12), Sn(1)–
Se(1)–Sn(3) 94.531(10), Sn(1)–Se(2)–Sn(2) 94.795(11), Sn(2)–Se(3)–Sn(3) 94.928(10),
Se(2)–Sn(1)–Se(1) 111.868(11), Se(2)–Sn(2)–Se(3) 110.224(11), Se(3)–Sn(3)–Se(1)
112.718(12), Si(1)–C(1)–Sn(1) 120.29(13), Si(1)–C(2)–Sn(2) 118.53(12), Si(1)–C(3)–
Sn(3) 119.35(14).
The environments about the tin atoms are distorted tetrahedral, with angles at Sn(1) varying
between 105.24(7) and 111.868(11)◦, corresponding, respectively to, C(11)–Sn(1)–Se(1)
and Se(2)–Sn(1)–Se(1), at Sn(2) varying between 102.61(7) and 114.66(10)◦, correspond-
ing, respectively to, C(21)–Sn(2)–Se(3) and C(21)–Sn(2)–C(2), and at Sn(3) varying be-
tween 106.65(7) and 112.718(12)◦, corresponding, respectively to, C(31)–Sn(3)–Se(3) and
Se(3)–Sn(3)–Se(1). The distortions from the ideal tetrahedral geometry are not significant.
This adamantane structure consists of three bridging Se atoms in which the Sn–Se–
Sn angles are very similar, equal to Sn(1)-Se(1)–Sn(3) 94.531(10)◦, Sn(1)–Se(2)–Sn(2)
94.795(11)◦, and Sn(2)–Se(3)–Sn(3) 94.928(10)◦. These angles are slightly smaller than
those corresponding in [(MeSeSn)2CMe2]2, with angles of (Sn1–Se1–Sn2) 99.18(7)◦ and
(Sn1–Se2–Sn2) 99.24(7)◦[10] and larger than those corresponding in [(SnR1)2Se2Cl2],
[(SnR1)3Se4Cl], and [(SnR1)4Se6] (R1 = CMe2CH2C(O)Me), with angles respectively of
84.52(3), 81.50(2)–83.26(2), and 85.55(1)–85.73(1)◦.[54] All Se–Sn–Se angles are similar
equal to (Se2–Sn1–Se1) 111.868(11)◦, (Se2–Sn2–Se3) 110.224(11)◦, Se(3)–Sn(3)–Se(1)
112.718(12)◦. These latter angles are comparable to those in [(MeSeSn)2CMe2]2, with
160
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
angles of (Se1–Sn1–Se2) 109.89(8)◦ and (Se1–Sn2–Se2) 111.31(9)◦[10] and larger than
those in [(SnR1)2Se2Cl2], [(SnR1)3Se4Cl], and [(SnR1)4Se6] (R1 = CMe2CH2C(O)Me),
with angles respectively of 95.48(3), 93.78(2)–94.14(2), and 94.03(1)–94.68(1)◦.[54]
The overall symmetrical characteristic of the molecular structure of 34 is confirmed by the
similarity of the angles at the silicon methylene tin bridges, equal to Si(1) – C(1) – Sn(1)
120.29(13)◦, Si(1) – C(2) – Sn(2) 118.53(12)◦, and Si(1) – C(3) – Sn(3) 119.35(14)◦. This
refers to the tripod geometry characteristic of these novel organotin precursors, in which
the Si-C-Sn bridges are all similar with distances of 1.858(3), 1.870(3), 1.868(3), 2.124(3),
2.134(3), and 2.135(3) Å, respectively corresponding to Si(1)–C(1), Si(1)–C(2), Si(1)–
C(3), Sn(1)–C(1), Sn(1)–C(2), Sn(1)–C(3). The S–Sn–S bridges are almost symmetrical
with bond distances equal to 2.5354(3) Å (Sn1–Se1), 2.5353(3) Å (Sn1–Se2), 2.5208(3)
Å (Sn2–Se2), 2.5473(3) Å (Sn2–Se3), 2.5323(3) Å (Sn3–Se1), and 2.5209(3) Å (Sn3–
Se2). These bond distances are similar to those corresponding in [(MeSeSn)2CMe2]2
equal to (Sn1–Se1) 2.496(2) Å and (Sn1–Se2) 2.506(2) Å,[51] and comparable to those
in [(SnR1)4Se6] (R1 = CMe2CH2C(O)Me), with distances varying between 2.5156(3)-
2.5954(3) Å.[54]
The identity of compound 34 is retained in solution. The compound is kinetically inert
on the 1H, 13C, 29Si and 119Sn NMR time scales. Thus, a 1H NMR spectrum (CDCl3
solution, see Supporting Information, Chapter 4, Figure S87) shows the resonance sig-
nal of SiCH3 protons appearing at δ 0.36 ppm (4J(1H – 117/119Sn) = 10 Hz, 2J(1H – 29Si) =
20 Hz. The SiCH2 protons, with integration of 6H, appear at δ 0.90 ppm (2J(1H – 117/119Sn)
= 72 Hz, 3J(1H – 77Se) = 122 Hz). The complex pattern referring to the protons of the
phenyl groups appears at δ 7.42-7.72 ppm with integration of 15H. In a 13C NMR spec-
trum (CDCl3 solution, see Supporting Information, Chapter 4, Figures S88), the reso-
nances corresponding to the SiCH2Sn carbon atoms appear at δ 5.23 ppm (1J(13C – 29Si)
= 52 Hz, 1J(13C – 117/119Sn) = 245/256 Hz) and those of the SiCH3 at δ 9.37 ppm
(3J(13C – 117/119Sn) = 43 Hz, 1J(13C – 29Si) = 85 Hz). In the aromatic part, the Cm reso-
nance appears at δ 128.9 ppm (3J(13C – 117/119Sn) = 61 Hz), the Cp at δ 130.07 ppm (13C-
117/119Sn) = 15 Hz, 5J(13C – 77Se) = 56 Hz), the Co at δ 134.4 ppm (2J(13C – 117/119Sn)
= 57 Hz), and the Ci at δ 140.67 ppm (3J(13C – 117Sn) = 10 Hz, 3J(13C – 77Se) = 52 Hz,
1J(13C – 117/119Sn) = 547/571 Hz). A 29Si NMR spectrum (CDCl3 solution, see Support-
ing Information, Chapter 4, Figure S89) shows a resonance referring to the MeSi silicon
atom at δ 13.8 ppm (2J(29Si – 117/119Sn) = 41 Hz, 1J(29Si – 13C) = 87 Hz). The 119Sn NMR
spectrum of a crystalline material of 34 in CDCl3 solution (Figure 77) shows a resonance
at δ 2.44 ppm (1J(119Sn – 77Se) = 1231 Hz, 1J(119Sn – 13Ci) = 573 Hz, 2J(119Sn – 117Sn) =
217 Hz) referring to three equivalent tin atoms which matches perfectly with the molecular
structure proposed for the solid state (Figure 76). This signal is similar to that at δ 3.1 ppm
(2J(119Sn – 117Sn) = 220 Hz),[10] reported for the stannaadamantane [(PhSeSn)2CH2]2 and
161
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
low-frequency-shifted compared to the corresponding Sn atoms in [(MeSeSn)2CMe2] at
δ 42.9 ppm (2J(119Sn – 117Sn) = 195 Hz).[10]
Figure 77. 119Sn NMR spectrum (149.26 MHz, CDCl3) of compound 34.
162
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 78. 77Se NMR spectrum (223.85 MHz, CDCl3) of compound 34.
The 77Se NMR spectrum of the same sample in CDCl3 (Figure 78) shows a resonance
at δ –346.75 ppm (1J(77Se – 117/119Sn) = 1168/1225 Hz). This resonance is similar to that
reported for the stannaadamantane [(MeSeSn)2CMe2] at δ –362 ppm (1J(77Se – 119Sn)
= 1255 Hz),[10] and low-frequency-shifted comparing to the corresponding Se atoms in
[(PhSeSn)2CH2]2 at δ –323 ppm (1J(77Se – 119Sn) = 1274 Hz).[10] An ESI-MS spectrum
(positive mode) of 34 shows one mass cluster centred at m/z 2163.07 corresponding to
the cations [C66H74O9Si3Sn9]2+ {[MeSi(CH2SnPhO)3]3 + 2H+}2+. This refers to the
polymerization process in solution via formation of the monomer-oxido-stannaadamantane
in solution. This is in relation with the formation mechanism suggested for the oxo clusters
29 and 30 (See Supporting Information, Chapter 4, Figures S93- S95).
The 119Sn NMR spectrum in CDCl3 of a white residue, obtained from a reaction between
one molar equiv of the diorganotin diiodido derivative 11 and 3.2 molar equiv of Na2S in
acetone/methanol/water solution shows one singlet resonance at 152 ppm with a coupling
constant 2J(119Sn – 117Sn) = 200 Hz (Figure 79). A crystalline material is isolated from
diethylether/dichlormethane solution as transparent needles suitable for X-ray diffraction
163
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
study. The compound 35, 7-methyl-1,3,5-tris((trimethylsilyl)methyl)-2,4,9-trithia-7-sila-
1,3,5-tristannaadamantane, MeSi[CH2Sn(CH2SiMe3)S]3 (Scheme 31) is isolated. This
latter shows good solubility in organic solvents.
Figure 79. 119Sn NMR spectrum (149.26 MHz, CDCl3) of the crude mixture of the reac-
tion of formation of 35.
Scheme 31. Synthesis of the S-silastannaadamantane MeSi(CH2SnCH2SiMe3S)3, 35.
Si
Sn
Sn
Sn
CH2SiMe3
Me3SiH2C S
S
S
Me
Me3SiH2C
Si
Me
Sn
Sn
Sn
I
I
Me3SiH2C
Me3SiH2C
I
I
CH2SiMe3
I
I
3 Na2S 
acetone/ MeOH/ H2O
  6 NaI
11 35
Figure 80 shows the molecular structure of compound 35. The figure caption contains
selected interatomic distances and angles. Compound 35 crystallizes in the monoclinic
space group P21/c, with two molecules in the unit cell. It shows an almost perfect sym-
metric adamantane-type structure rather similar to that of its phenyl-substituted analogue,
compound 33.
164
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 80. POV-Ray image of the molecular structure of MeSi[CH2Sn(CH2SiMe3)S]3, 35.
Protons are omitted for clarity. Selected interatomic distances (Å): Sn(1)–S(1) 2.417(3),
Sn(2)–S(1) 2.416(2), Sn(1)–S(2) 2.416(2), Sn(3)–S(2) 2.394(2), Sn(2)–S(3) 2.425(2),
Sn(3)–S(3) 2.428(2). Selected interatomic angles (◦): C(11)–Sn(1)–S(2) 101.9(3), C(11)–
Sn(1)–C(1) 115.6(4), Sn(1)–S(1)–Sn(2) 100.00(9), Sn(1)–S(2)–Sn(3) 100.61(9), Sn(2)–
S(3)–Sn(3) 100.45(9), S(1)–Sn(1)–S(2) 107.47(9), S(1)–Sn(2)–S(3) 110.91(8), S(2)–
Sn(3)–S(3) 106.51(9), Si(1)–C(1)–Sn(1) 117.9(5), Si(1)–C(2)–Sn(2) 118.5(4), Si(1)–C(3)–
Sn(3) 120.2(5).
The environments about the tin atoms are distorted tetrahedral, with angles, varying
from 101.9(3) and 115.6(4)◦, corresponding, respectively to, C(11)–Sn(1)–S(2) and C(11)–
Sn(1)–C(1). The distortions from the ideal tetrahedral geometry are not significant.
Like compound 33, this adamantane structure consists of three bridging S atoms in
which the Sn – S – Sn angles are very similar, equal to Sn(1)–S(1)–Sn(2) 100.00(9)◦,
Sn(1)–S(2)–Sn(3) 100.61(9)◦, and Sn(2)–S(3)–Sn(3) 100.45(9)◦. All S–Sn–S angles
are similar equal to (S1–Sn1–S2) 107.47(9)◦, (S1–Sn2–S3) 110.91(8)◦, S(2)–Sn(3)–S(3)
106.51(9)◦. The overall symmetrical characteristic of the molecular structure of 35 is
confirmed by the similarity of the angles at the silicon methylene tin bridges, equal
to Si(1) – C(1) – Sn(1) 117.9(5)◦, Si(1) – C(2) – Sn(2) 118.5(4)◦, and Si(1) – C(3) – Sn(3)
120.2(5)◦. The Sn – S – Sn bridges are almost symmetrical with bond distances equal to
2.417(3) Å (Sn1–S1), 2.416(2) Å (Sn2–S1), 2.416(2) Å (Sn1–S2), 2.394(2) Å (Sn3–S2),
2.425(2) Å (Sn2–S3), and 2.428(2) Å (Sn3–S3).
165
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
As well, the molecular structure of 35 suggested in solid state is retained in solution.
Compound 35 is kinetically inert on the 1H, 13C, 29Si and 119Sn NMR time scales (See
Supporting Information, Chapter 4, Figures S98- S102). The 119Sn NMR spectrum of a
crystalline material of 35 in CDCl3 solution (Figure 81) shows a resonance at δ 152 ppm
(2J(119Sn – 117Sn) = 212 Hz, 4J(119Sn – 117Sn) = 3614 Hz) referring to three equivalent tin
atoms which matches perfectly with the molecular structure proposed in solid state. This
signal is similar to that corresponding in the stannaadamantane [(CH2SiMe3SSn)2CH2]2
at δ 159.4 ppm (2J(119Sn – 117Sn) = 195 Hz).[10] A 29Si NMR spectrum (CDCl3 solution,
see Supporting Information, Chapter 4, Figure S102) shows two resonances referring to
the MeSi and the CH2SiMe3 silicon atoms, respectively, at δ 11.3 ppm (2J(29Si – 117/119Sn)
= 52 Hz), and δ 2.2 ppm (2J(29Si – 117/119Sn) = 30 Hz, 1J(29Si – 13C) = 56 Hz).
An ESI-MS spectrum (positive mode, see Supporting Information, Chapter 4, Figures
S103, S104) of 35 shows one intense mass clusters centred at m/z 798.8659 corresponding
to the cation [C16H43S3Si4Sn3]+ MeSi[CH2Sn(CH2SiMe3)S]3 + H++ which confirms that
the cluster remains intact in solution even under harsh ESI-MS conditions.
Figure 81. 119Sn NMR spectrum (149.26 MHz, CDCl3) of compound 35.
166
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
We wanted to investigate whether there is an exchange reaction undergoing in solution
between the compounds MeSi(CH2SnPhS)3, 33, and MeSi(CH2SnPhSe)3, 34, in CDCl3
and C6D6. Furthermore, we studied the reaction of the Se-containing adamantane, 34,
with elemental sulphur, S8, in CDCl3. Such redistribution reactions have not been fairly
investigated for stannaadamantane compounds.[53]
A 119Sn NMR spectrum measured 24h after equimolar quantities of of 33 and 34 had been
mixed in CDCl3-solution shows the following signals (assigned to according to Scheme
32): δ 2.9 ppm (A), δ 98.9 ppm (B), at δ 0.3 and 52.6 ppm with integral ratio of 1:2 (C),
and δ 100.4 and 50.5 ppm with integral ratio of 1:2 (D).
Scheme 32. Different intermediate species (A, B, C, and D) formed in course of the
redistribution reaction between 33 and 34 in CDCl3.
Si
Sn
Sn
Sn Ph
Ph S
S
S
Me
Ph
Si
Sn
Sn
Sn Ph
Ph Se
Se
Se
Me
Ph
+
Si
Sn
Sn
Sn Ph
Ph S
Se
S
Me
Ph
Si
Sn
Sn
Sn Ph
Se
S
Se
Me
Ph
Ph
+
CDCl3
A B
DC
I
167
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 82. 119Sn NMR spectra (223.85 MHz, CDCl3) of redistribution reactions of 33 and
34.
We performed 119Sn NMR measurements over a period of 78 days. Figure 82 represents
the corresponding 119Sn NMR spectra measured over this period of time. The diagram
shown in Figure 83, presenting the integration of each species over this period of time. It
shows approximately a consumtion of A (14.5 %) and B (16.2 %) at day 78, in favour for
the formation of C and D with a slight domination of species D (37.5 %) in comparison to
that of species C (31.3 %).
168
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 83. Kinetic study of redistribution reactions of 33 and 34 in CDCl3 (Integration %
= f(t)).
The 119Sn NMR spectrum recorded at day 21 (Figure 84), taken as example, shows
the two signals corresponding to species C at δ 0.3 ppm (1J(119Sn – 77Se) = 1209 Hz,
2J(119Sn – 117/119Sn) = 217/227 Hz, 2J(119Sn – 29Si) = 48 Hz) (Figure 85) , which refers
to the one SnSe2 atom in (C), and at δ 52.6 ppm (1J(119Sn – 77Se) = 1683 Hz,
2J(119Sn – 117Sn) = 185 Hz, 2J(119Sn – 117/119Sn) = 218/229 Hz, 1J(119Sn – 13Ci) = 781 Hz,
3J(119Sn – 13Cm) = 69 Hz, 2J(119Sn – 29Si) = 48 Hz) (Figure 86), which refers to the
two SeSnS atoms in (C). The two resonance signals corresponding to species D ap-
pear at δ 100.4 ppm (2J(119Sn – 117/119Sn) = 185/195 Hz, 2J(119Sn – 29Si) = 48 Hz),
the 3J(119Sn – 77Se) is not detected (Figure 87), which refers to the one SnS2 atom
in (D) , and at δ 50.5 ppm (1J(119Sn – 77Se) = 1683 Hz, 2J(119Sn – 117Sn) = 218 Hz,
2J(119Sn – 117/119Sn) = 186/195 Hz, 1J(119Sn – 13Ci) = 781 Hz, 3J(119Sn – 13Cm) = 69 Hz,
2J(119Sn – 29Si) = 48 Hz) (Figure 86), which refers, as well, to the two SnSSe atoms in
(D). These earlier mentioned NMR shifts and coupling constants are very near to the
corresponding shifts in the species resulting from the redistribution reaction between
[CH2(SnSPh)2]2 and [CH2(SnSePh)2]2.[10]
169
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 84. A 119Sn NMR spectrum (223.85 MHz, CDCl3) of a solution containing equimo-
lar amounts of 33 and 34 at day 21.
Figure 85. Cut-out of an 119Sn NMR spectrum (223.85 MHz, CDCl3) showing the signal
for the SnSe2 atom in (C).
170
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 86. Cut-out of an 119Sn NMR spectrum (223.85 MHz, CDCl3) showing the signals
for species C+D.
Figure 87. Cut-out of an 119Sn NMR spectrum (223.85 MHz, CDCl3) showing the signal
for the SnS2 atom in (D).
171
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 88. 77Se NMR spectrum (114.48 MHz, CDCl3) of a solution containing equimolar
amounts of 33 and 34 (day 21).
The resonance shift corresponding to the species A [MeSi(CH2SnSe)3] appears at
δ 2.9 ppm (1J(119Sn – 77Se) = 1217 Hz, 1J(119Sn – 13Ci) = 571 Hz, 2J(119Sn – 117Sn) =
214 Hz, 3J(119Sn – 13Cm) = 68 Hz, 2J(119Sn – 29Si) = 48 Hz) (Supporting Information
Chapter 4, Figure S106). As to the resonance shift corresponding to the specie B
[MeSi(CH2SnS)3] appear at δ 98.9 ppm (4J(119Sn – 115Sn) = 291 Hz, 2J(119Sn – 117Sn)
= 187 Hz, 1J(119Sn – 13Ci) = 639 Hz, 3J(119Sn – 13Cm) = 71 Hz, 2J(119Sn – 29Si) = 50 Hz)
(See Supporting Information, Chapter 4, Figure S107). The 77Se NMR spectrum of the
same sample (Figure 88) shows three signals at δ –346.7, –346.5 (1J(77Se – 117/119Sn) =
1221/1163 Hz), and –346.2 ppm, referring to, respectively, the one SeSn atom in (D), the
three SeSn atoms in (A), and the two SeSn atoms in (C). The 1J(77Se – 117/119Sn) coupling
constants for species C and D were not determined. Table 9 summarizes the 119Sn and 77Se
NMR data of species A, B, C, and D resulting from the redistribution reactions between
33 and 34 in CDCl3.
172
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Table 9. Summary of 119Sn and 77Se NMR Data and coupling constants for Species A, B,
C, and D presented in the exchange reaction between 33 and 34 in CDCl3.
Species δ (119Sn) δ (77Se) 1J(119Sn–77Se) 2J(119Sn–117Sn)
ppm ppm Hz Hz
A 2.9 –346.5 1217 214
B 98.9 — — 187
C 0.3, 52.6 –346.2 1209, 1683 185
D 50.5, 100.4 –346.7 1683 218
Species 2J(119Sn–117/119Sn) 2J(119Sn–29Si) 1J(119Sn–13C) 3J(119Sn–13Cm)
Hz Hz Ci, – (CH2) – Hz
Hz
A — 47 570 68
B — 50 639, 291 71
C 218/229 48 781 69
D 186/195 48 781 69
A 119Sn NMR spectrum measured 24 h after equimolar amounts of 33 and 34 had been
dissolved in C6D6, shows rather similar signals as observed for the corresponding mixture
in CDCl3 (δ 2.59 ppm, species A; δ 100.1 ppm, species B; δ 0.23 and 53.06 ppm with
integral 1:2, species C; δ 101.7 and 50.95 ppm with integral 1:2, species D), (Scheme 33).
These signals have the same coupling constants mentioned for the intermediate species
A, B, C, and D in the previous redistribution reaction in CDCl3. This is also valid for the
77Se NMR spectrum of this reaction mixture.
173
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Scheme 33. Different intermediate species (A, B, C, and D) formed during the exchange
reaction between 33 and 34 in C6D6.
Si
Sn
Sn
Sn Ph
Ph S
S
S
Me
Ph
Si
Sn
Sn
Sn Ph
Ph Se
Se
Se
Me
Ph
+
Si
Sn
Sn
Sn Ph
Ph S
Se
S
Me
Ph
Si
Sn
Sn
Sn Ph
Se
S
Se
Me
Ph
Ph
+
C6D6
A B
DC
II
33 34
Figure 89. 119Sn NMR spectra (223.85 MHz, C6D6) of redistribution reactions of 33 and
34.
174
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 90. Kinetic study of redistribution reactions of 33 and 34 in C6D6: (Integration %
= f(t)).
The 119Sn NMR measurements were performed over a period of 39 days. Figure 89 rep-
resents the corresponding 119Sn NMR spectra measured over this period of time. Figure
90 shows the kinetic study of the redistribution reaction between 33 and 34 in C6D6:
(Integration % = f(t)).
We notice that the reaction is kinetically much faster than that in CDCl3 and there is a
slight domination of the selenide-species in comparison to those of sulfide. At day 39 the
integration of each specie is equal to 15 % for (A), 10 % for (B), 40 % for (C), and 35 %
for (D).
Scheme 34 shows the redox reaction in CDCl3 between compound 34 and elemental
sulfur, S8, in the molar ratio 1:1. A 119Sn NMR spectrum measured after 24 h shows
three signals at 2.46, -0.26, and 52.2 ppm, respectively, referring to species A and C. After
one week, the same species B, C, and D appear, as in the redistribution reaction shown
in Scheme 33. The Se-containing stannaadamantane 34 almost completely disappeared
and elemental selenium precipitated. The 119Sn NMR spectrum shows almost the same
NMR shifts resonances at δ 2.46 ppm (specie A), δ 98.6 ppm (specie B), δ 0.26, 52.1
ppm (species C; [MeSi(CH2Sn)3Se2S]), with integration of 1:2, and δ 100.7, 50.09 ppm
(species D; [MeSi(CH2Sn)3SeS2]), with integration of 1:2. These signals have the same
coupling constants mentioned for the intermediate species A, B, C, and D in the previous
redistribution reactions. This is also valid for the 77Se NMR spectrum of this reaction
mixture.
175
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Scheme 34. Different intermediate species (A, B, C, and D) formed during the redox
reaction between 34 with S8 in CDCl3.
Si
Sn
Sn
Sn Ph
Ph S
S
S
Me
Ph
Si
Sn
Sn
Sn Ph
Ph Se
Se
Se
Me
Ph
+
Si
Sn
Sn
Sn Ph
Ph S
Se
S
Me
Ph
Si
Sn
Sn
Sn Ph
Se
S
Se
Me
Ph
Ph
+
CDCl3
A
B DC
S8
+
34
+ Se
Figure 91. 119Sn NMR spectra (223.85 MHz, CDCl3) of redox reactions of 34 with S8 in
1:1 ratio.
176
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 92. Kinetic study of redox reactions of 34 with S8 in CDCl3: (Integration % = f(t)).
The 119Sn NMR measurements was realized over a period of 53 days. Figure 91 represents
the corresponding 119Sn NMR spectra measured over this period of time. Figure 92 shows
the kinetic study of the redox reaction of 34 with S8 in CDCl3: (Integration % = f(t)). We
notice that the reaction is slower than the redistribution reactions. However, it ends with
a total consumption of species (A) Se-containing silastannaadamantane. There is a clear
domination of the sulfur-containing-species in comparison to those of selenium-containing
species. At Day 53, the integration of each specie is equal to 0 % for (A), 40 % for (B),
18 % for (C), and 42 % for (D).
No detailed studies have been performed concerning the mechanisms that account for the
redistribution and redox-type reactions shown in Schemes 32, 33, and 34, respectively.
The fact that the redistribution reaction between 33 and 34 is, with caution, apparently
faster in C6D6 than in CDCl3 makes protons less likely being involved in the mechanism.
Chloroform usually contains trace amounts of protons. One hypothesis is that a bimolec-
ular mechanism accounts for the redistribution reaction.[55] Compounds 33 and 34 form
a Lewis base – Lewis acid adduct via intermolecular SSn and SeSn interactions as
shown in Scheme 35.
177
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Scheme 35. Possible intermediate (or transition state) involved in the redistribution reac-
tion between 33 and 34.
Se
Sn Se
Sn
SeSn
Si
Me
Ph
Ph
Ph
Sn
S
Sn
S
Sn
S
Si
Me
Ph
Ph
Ph
One way to check this hypothesis is recording variable time 119Sn NMR spectra at different
concentrations. In addition, DFT calculation could be performed to check whether the
adduct shown in Scheme 35 is in a thermodynamic minimum or not. However, this could
not be done in course of the work done for this PhD thesis.
A similar intermediate can be assumed being involved in course of the redox reaction
between compound 34 and elemental sulfur. The S8 molecule coordinates to a tin centre
of 34 followed by a single electron transfer (Scheme 36).
Scheme 36. Possible intermediate (or transition state) involved in the redox reaction be-
tween compound 34 and elemental sulfur, S8.[56]
Sn
Se
Sn
Se
Sn
Se
Si
Me
Ph
Ph
Ph
S
S
S S
S
S
SS
One characteristic of compounds 33–35 is UV-Vis emission. Figure 93 represents the
calculated emission for UV as a function of the fundamental electronic transition energy.
It shows that the intermediate species C and D have more potential for UV emission than
that of A (compound 34) and B (compound 33). In addition, the trimethylsilylmethyl-
substituted silastannadamantane intermediates, theoretically have weak UV emission ca-
pacity (Figure 93).
178
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Figure 93. Calculated Spectral emission characteristics of 33 (B), 34 (A) and the interme-
diates (C) and (D): UV (a.u) = f(Energy).
Figure 94. Calculated Spectral emission characteristics of the CH2SiMe3-substituted silas-
tannadamantane theoretical intermediates: UV (a.u) = f(Energy).
4.4 Conclusion
In conclusion we have shown that simple tripod-type diorganotin halides
MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph, CH2SiMe3) serve as
precursors for unprecedented ladder-like containing diorganotin oxo clusters. Among
these, the novel belt-shaped molecular diorganotin oxides [MeSi(CH2SnRO)3]n of
unprecedented oktokaideka (n = 18) and trikonta (n = 30) nuclearity are striking. The
results obtained fit well into the ongoing interest in large-sized metaloxo clusters in
179
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
general[57] and tinoxo clusters of high nuclearity in particular.[58] The concept shown
herein holds great potential for future work. Just to mention a few options out of many,
variation of the substituents R and/or replacing the CH3 group with other substituents,
variation of the spacing between the silicon and tin centres as well as replacement of
the MeSi bridgehead moiety with MeGe or with isoelectronic P, P=E (E –– O, S, Se) or
PM (M = transition metal moiety such as W(CO)5 and others) might give a plethora of
novel diorganotin oxides showing polynuclear structures. Moreover, replacing the organic
substituent R in Roesky’s (RSn)4O6 (R = (Me3Si)2CH)[59] to a R'of slightly reduced
steric bulk could give well defined oligomers [(R'Sn)4O6]n similar to 29 and 30.[45] As
well, these same precursors hold potential to form first silicon containing Sulfur- and
selenium adamantane-like structures, which have interesting exchange reactions that can
be subject of future work focusing on the reactional mechanisms taking place.
4.5 Experimental section
• Synthesis of [(MeSi(CH2)3)Sn(µ3-O)3(Ph)Sn(Cl)(Ph)Sn(µ2-OH)(Ph)Sn(t-
Bu)2]2 (26)
To a solution of 4 (263.00 mg, 0.279 mmol) in 30 mL of CHCl3 was added to three equiv
molar of freshly synthesized t-Bu2SnO (221.85 mg, 0.891 mmol).[51,60] The resulting mix-
ture was stirred at room temperature overnight. Chloroform was removed in vacuo (10−3
mmHg) and t-Bu2SnCl2 was washed out successively with iso-hexane. We obtain a white
residue. Recrystallization of this latter from CH2Cl2/ iso-hexane gives 142 mg (47 %)
of pure 5 as transparent needles, mp 382 ◦C. 1H NMR (C6D6, 600.29, 298 K): δ 0.075
(2J(1H – 117/119Sn) = 81 Hz, 2J(1H – 1H) = 13 Hz, 2H, SiCH2Sn), 0.215 (2J(1H – 117/119Sn)
= 68 Hz, 2J(1H – 1H) = 13 Hz, 2H, SiCH2Sn), 0.52 (2J(1H – 117/119Sn) = 80 Hz, 2J(1H – 1H)
= 13 Hz, 2H, SiCH2Sn), 0.805 (2J(1H – 117/119Sn) not measured, 2J(1H – 1H) = 13 Hz, 2H,
SiCH2Sn), 2.17 ppm (2J(1H – 117/119Sn) = 126 Hz, 2J(1H – 1H) = 13 Hz, 2H, SiCH2Sn),
2.37 (2J(1H – 117/119Sn) = 106 Hz, 2J(1H – 1H) = 13 Hz, 2H, SiCH2Sn), 0.78 (s, 6H,
SiCH3), 1.07, 1.63 (s, 36H, 3J(1H – 117/119Sn) = 116 Hz, t-Bu2SnCl), 6.98–8.27 (com-
plex pattern, 30H, Ph). 13C{1H} NMR (C6D6, 150.94, 298 K): δ 5.5 (3J(13C – 117/119Sn)
= 53 Hz, 1J(13C – 29Si) = 74, SiCH3), 7.6 (1J(13C – 117/119Sn) = 464 Hz, SiCH2Sn),
11.4 (1J(13C – 117/119Sn) = 517 Hz, SiCH2Sn) , 18.1 (1J(13C – 117/119Sn) = 503 Hz,
SiCH2Sn), 41.4 (1J(13C – 117/119Sn) = 568 Hz, SiCH2Sn), 42.0 (1J(13C – 117/119Sn) =
576 Hz, SiCH2Sn), 30.5, 31.6 (t-Bu2SnCl), 128.7, 128.8, 128.9 (Cm), 130.23, 130.26,
130.4 (4J(13C – 117/119Sn) = 14 Hz, Cp), 136.2, 136.7, 137.1 (2J(13C – 117/119Sn) = 59 Hz,
Co), 143.9, 144.61, 144.67 (1J(13C – 117/119Sn) = 759/805 Hz, Ci). 29Si NMR (C6D6,
119.26, 298 K): δ 3.32 (2J(29Si – 117/119Sn) = 63 Hz, SiCH3). 119Sn NMR (CDCl3,
223.85, 298 K): δ –195 (2J(119Sn3A – 117/119Snexo) = 298 Hz, 2J(119Sn3A – 117Snendo)
= 180 Hz, 2J(119Sn3A – 29Si) = 62 Hz), Sn(3A)), -208 (2J(119Sn2 – 117/119Snendo) =
180
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
243 Hz, 2J(119Sn2 – 117Snendo) = 90 Hz), Sn(2)), -228 (2J(119Sn1 – 117Snendo) = 99 Hz,
2J(119Sn1 – 117/119Snexo) = 285 Hz, 2J(119Sn2 – 117/119Snendo) = 209 Hz, Sn(1)), -230
Sn(4A). Anal. Calcd (%) for C60H86Cl2Si2Sn8: C 35.82 H 4.31 Found: C 35.9, H 4.3.
Electrospray MS: m/z (%) positive mode: 2012.7 (100, [M + H+]+). IR (cm−1): ν(Sn–O–
Sn) 695-726; ν(Sn–C) 539-562, and ν(OH) 2924- 2849.
• Synthesis of {[MeSi(CH2)3]SnCl(CH2SiMe3)(µ3-O)SnCl(CH2SiMe3)Sn(µ3-
O)(Cl)2(CH2SiMe3)Sn(t-Bu)2} (27)
To a solution of 12 (58.00 mg, 0.062 mmol) in 30 mL of CHCl3 was added to three equiv
molar of freshly synthesized t-Bu2SnO (139.59 mg, 0.186 mmol).[51,60] The resulting mix-
ture was stirred at room temperature overnight. Chloroform was removed in vacuo (10−3
mmHg) and (t-Bu2SnOHCl)2 was washed out successively with iso-hexane. We obtain a
white residue. Recrystallization of this latter from CH2Cl2/ iso-hexane gives 30 mg (42 %)
of pure 27 as transparent needles, mp 160 ◦C. 1H NMR (C6D6, 600.29, 298 K): δ 0.21,
0.26, 0.27 (12H, SiCH2Sn), 1.24–1.36 (complex pattern, 30H, SiCH3), 1.38, 1.41 (18H,
t-Bu2Sn). 29Si NMR (C6D6, 119.26, 298 K): δ –21.8 (SiCH3), 0.81, 1.3, 1.5 (CH2SiMe3).
119Sn NMR (C6D6, 223.85, 298 K): δ –218 (2J(119Sn4 – 117/119Snendo) = 208 Hz,
Sn(4)), -158 (2J(119Snendo – 117Snendo) = 125 Hz, Snendo), -149 (2J(119Sn1 – 117/119Snendo))
= 214 Hz), Sn(1)), -132 (Snendo). Anal. Calcd (%) for C24H64Cl4O2Si4Sn4 + 3 (t-
Bu2SnO)3: C 34.38, H 6.7. Found: C 34.4, H 6.4. Electrospray MS: m/z (%) posi-
tive mode: 793.1270 [C16H45Cl2OSi4Sn3]+{[MeSi(CH2SnCH2SiMe3)3(O)Cl2] + H+}+,
807.1418 [C16H44Cl2O2Si4Sn3]+ {[MeSi(CH2SnCH2SiMe3)3(O)Cl2] + (µ3-O)}+.
• Synthesis of {[MeSi(CH2)3]SnI(CH2SiMe3)(µ2-OH)[SnO(CH2SiMe3)]2Sn(µ2-
OH)ISn(t-Bu)2} (28)
To a solution of 11 (863 mg, 0.589 mmol) in 50 mL of CHCl3 was added to one equiv
molar of freshly synthesized t-Bu2SnO (440 mg, 0.589 mmol).[51,60] The resulting mix-
ture was stirred at room temperature overnight. Chloroform was removed in vacuo (10−3
mmHg) and (t-Bu2SnOHCl)2 was washed out successively with iso-hexane. We obtain a
white residue. Recrystallization of this latter from CH2Cl2/ iso-hexane gives 444 mg
(60 %) of pure 28 as transparent needles, mp 156-165 ◦C. 1H NMR (CDCl3, 600.29,
298 K): δ 0.12, 0.27 (12H, SiCH2Sn), 0.17, 0.20, 0.20 (30H, SiCH3), 1.36, 1.42, 1.42
(18H, t-Bu2Sn). 13C{1H} NMR (CDCl3, 150.94, 298 K): δ 1.58, 2.2, 2.51 (SiCH3), 1.44
(SiCH2Sn), 29.1, 30.3, 30.5 (t-Bu2Sn). No coupling constants are determined given the
quality of the NMR spectra for such compounds. No further measurements could be real-
ized within the tine frame of this PhD: 29Si NMR (CDCl3, 79.26, 298 K): δ –21 (SiCH3),
0.72, 1.42, 1.58 (CH2SiMe3). 119Sn NMR (CDCl3, 149.26, 298 K): δ –183.5, -183.2
(2J(119Snexo-117/119Snendo) = 248 Hz, Sn(1), Sn(4)), -156 (2J(119Snendo – 117Snendo) =
167 Hz, Snendo), -150 (2J(119Snexo-117/119Snendo) = 242 Hz, Snendo). Anal. Calcd (%)
for C24H62I2O4Si4Sn4: C 29.96, H 4.98. Found: C 22.9, H 5.0. Electrospray MS: m/z
(%) positive mode: 750.93 {10, [C16H43O3Si4Sn3]+}+: {[MeSi(CH2SnOCH2SiMe3)3] +
181
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
H+}+, 796.93 {100, [C16H43O3Si4Sn3]+ + 12 CH2Cl2}+: {[MeSi(CH2SnOCH2SiMe3)3] +
H+ + 12 CH2Cl2}+. IR (cm−1): ν(OH) 3656-3493, 2950-2850 cm−1.
• Synthesis of [MeSi(CH2SnPhO)3]6 (29)
To a solution of 3 (888.00 mg, 0.581 mmol, 1 equiv) in 30 mL of CHCl3 was added
freshly synthesized t-Bu2SnO (434.45 mg, 1.75 mmol, 3 equiv).[51,60] The resulting mix-
ture was stirred at room temperature overnight. Chloroform was removed in vacuo
(10−3 mmHg) and t-Bu2SnI2 was washed out successively with iso-hexane. A white
residue was obtained (433.54 mg, 98 %). Recrystallization of this latter from CH2Cl2/
diethyl ether gave transparent crystals suitable for X-ray diffraction analysis, mp over
400 ◦C. 1H NMR (CDCl3, 500.08, 298 K): δ 0.06 (2J(1H – 117/119Sn) 50 Hz, 2J(1H – 1H)
10 Hz)/0.48 (2J(1H – 117/119Sn) 70 Hz, 2J(1H – 1H) 10 Hz), 0.88 (2J(1H – 117/119Sn) 85 Hz,
2J(1H – 1H) 15 Hz)/1.20 (2J(1H – 117/119Sn) not measured, 2J(1H – 1H) 14.7 Hz), and 1.28
ppm (2J(1H – 117/119Sn) not measured, 2J(1H – 1H) 10 Hz)/1.91 (2J(1H – 117/119Sn) 120 Hz,
2J(1H – 1H) 10 Hz), 0.3, 1.42 (s, 18H, SiCH3), 6.65–7.72 (complex pattern, 90H, Ph).
13C{1H} NMR (CDCl3, 125.75, 298 K): δ 5.3, 29.1 (SiCH3), 7.5 (1J(13C – 29Si) = 80 Hz),
13.6, 14.6 (SiCH2Sn)), 127.5, 128.1, 128.4 (Cm), 129.4, 129.5 (we didn’t recognized the
third signal) (Cp), 135.3, 135.4, 135.7 (Co), 143.1, 143.9, 144.3 (Ci) we didn’t recog-
nized the 117/119Sn satellites fault of bad resolution of the spectrum. 29Si NMR no sig-
nal could be detected even with long measurement.119Sn NMR (CDCl3, 149.26, 298 K):
δ –204 2J(117/119Sn – 29Si) = 59 Hz), (2J(119Sn – 117Sn) = 180 Hz, 2J(119Sn – 117/119Sn)
= 315 Hz, -225 (2J(119Sn – 117/119Sn) = 315 Hz), -228 (2J(119Sn – 117Sn) = 180 Hz)
(SnPh). Anal. Calcd (%) for C132H144O18Si6Sn18: C 36.67 H 3.36 Found: C 35.9,
H 4.4. Electrospray MS: m/z (%) positive mode:1442.7312 C44H49O6Si2Sn6+ (100,
[MeSi(CH2SnPhO)3]2 +H+)+, 2161.5910 C66H73O9Si3Sn9+ (0.7, [MeSi(CH2SnPhO)3]3 +
H+)+, 3636.3600 C11H125O16Si5Sn15+ (2, [MeSi(CH2SnPhO)3]3 + MeOH + H+)+,
4324.1823 C132H145O18Si6Sn18+ ([MeSi(CH2SnPhO)3]6 + H+)+. IR (cm−1): ν(Sn–O-Sn)
695–726; ν(Sn-C) 494–559.
• Synthesis of [MeSi(CH2SnCH2SiMe3O)3]10 (30)
Over a period of 1h, a solution of NaOH in water (20mL) (83.25mg, 2.08 mmol, 6
equiv) was added to a solution of 11 (508.00 mg, 346.90 µmol, 1 equiv) in 50 mL of
acetone at 0 ◦C. The resulting mixture was stirred at room temperature overnight. All
solvents were removed in vacuo (10−3 mmHg) and NaI was washed out successively
with water. An oily residue (255.29 mg, 98 %) was obtained showing good solubility in
CHCl3 and CH2Cl2. Crystallization from CH2Cl2/ diethyl ether gave transparent crystals
suitable for X-ray diffraction analysis, mp 347 ◦C. 1H NMR (CDCl3, 600.29, 298 K):
δ 0.04–0.33 (complex pattern, 270H, CH2Si(CH3)3), 0.85-0.89 (complex pattern, 30H,
SiCH3), 1.26 (s, 60H, SiCH2Me3), 1.59 (s, 60H, SiCH2Sn). 13C{1H} NMR (CDCl3,
150.94, 298 K): δ 1.02-2.67 (SiCH3), 14.12, 22.69, 29.36, 31,12 (SiCH2Sn), 29.69
(CH2SiMe3). Even with long data acquisition, no 117/119Sn satellites were obtained .29Si
182
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
NMR (CDCl3, 119.26, 298 K): δ –21 (SiMe), -0.8-1.6 (CH2SiMe3). 119Sn NMR (CDCl3,
223.85, 298 K): δ –163-126 (SnCH2SiMe3). Anal. Calcd (%) for C160H420O30Si40Sn30:
C 25.59 H 5.64 Found: C 25.6, H 5.7. Electrospray MS: m/z (%) positive mode:
750.9293 C16H43O3Si4Sn3+ (2.5, [MeSi(CH2SnCH2SiMe3O)3] + H+)+, 768.8946
[MeSi(CH2SnCH2SiMe3O)3 + H2O + H+]+, 788.9056 [MeSi(CH2SnCH2SiMe3O)3 +
K+]+, 1646.8168 {[MeSi(CH2Sn(OH)2CH2SiMe3)3]2 + 2H2O + H+}+, 1669.6017
{[MeSi(CH2Sn(OH)2CH2SiMe3)3]2 + CH3CN + H2O + H+}+, 2254.7532
{[MeSi(CH2SnCH2SiMe3O)3]6 + 2H+}2+, 3077.6608 {[MeSi(CH2SnCH2SiMe3O)3]4 +
H+}+, 4506.3980 C96H253O18Si24Sn18+ (4, [MeSi(CH2SnCH2SiMe3O)3]6 + H+)+. IR
(cm−1): ν(Sn–O-Sn) 652–713; ν(Sn–C) 423–550.
• Synthesis of [MeSi(CH2SnBr)3(µ2-OH)2(µ4-O)(µ3-OEt)2]2 ·2EtOH (32)
A recrystallization attempt of the nonabromido-organotin compound
9, in an excess of EtOH in presence of dichloromethane gives
[MeSi(CH2SnBr)3(µ2-OH)2(µ4-O)(µ3-OEt)2]2 ·2EtOH, 32 as brownish needles
crystals. This crystalline material is insoluble in organic solvents and water. Anal.
Calcd (%) for C38H106 Br12O25Si4Sn12: (2C20H54 Br6O12Si2Sn6 + 2H2O – EtOH: C
13.2 H 3.09. Found: C 13.2, H 3.1. Electrospray MS: m/z (%) negative mode: 1610.3
[C20H57Br4O14Si2Sn6]– : (2.5, [M – Br2 + OH– + H2O]– ). IR (cm−1): ν(OH) 3501–3318,
2969-2893 cm−1.
• Synthesis of 7-Methyl-1,3,5-tris(triphenyl-2,4,9-trithio-7-sila-1,3,5-
tristannaadamantane: MeSi(CH2SnPhS)3 (33)
A (2.18 g, 1.52 mmol, 1 equiv) sample of 3 was dissolved in 100 mL acetone and added
dropwise to a magnetically stirred ice-cooled solution of Na2S ·9H2O (1.17 g, 4.87 mmol,
3.2 equiv) in water. The reaction mixture was stirred over night at room temperature, and
the precipitate was filtered off, dried in vacuo, giving 1 as amorphous white solid (1.17
g, 768.83 mmol, 98 % yield). Further purification was achieved by recrystallization from
dichloromethane - diethyl ether to give transparent needles.
1H NMR (CDCl3, 400.25, 298 K): δ 0.43 (s, 3H, 4J(1H – 117/119Sn) = 11 Hz, 2J(1H – 29Si)
= 20 Hz, SiMe), 0.80 (s, 6H, 2J(1H – 117/119Sn) = 72 Hz, SiCH2Sn), 7.42–7.77 (complex
pattern, 15H, Ph). 13C{1H} NMR (CDCl3, 100.46, 298 K): δ 5.41 (1J(13C – 117/119Sn)
=275/294 Hz, SiCH2Sn), 8.45 (1J(13C – 29Si) = Hz, SiMe), 128.96 (3J(13C – 117/119Sn) =
70 Hz, Cm), 130.19 (4J(13C – 117/119Sn) = 10 Hz, Cp), 134.47 (2J(13C – 117/119Sn) = 57 Hz,
Co), 141.49 (1J(13C – 117/119Sn) =615/645 Hz, Ci). 29Si NMR (CDCl3, 119.26, 298 K):
δ 13.4 (2J(29Si – 117/119Sn) = 50 Hz, 1J(29Si – 13C) = 94 Hz, CH2SiMe). 119Sn NMR
(CDCl3, 149.26, 298 K): δ 98 (2J(119Sn – 117Sn) = 190 Hz, SnPhS). Anal. Calcd (%) for
C22H24S3SiSn3: C 34.37, H 3.15. Found: C 34.3, H 3.3. Electrospray MS: m/z (%) positive
mode 793.5 (65, [M + Na+]+).
• Synthesis of 7-Methyl-1,3,5-tris(triphenyl-2,4,9-triselen-7-sila-1,3,5-
tristannaadamantane: MeSi(CH2SnPhSe)3 (34)
183
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
A (0.511 mg, 4.03 mmol, 3 equiv) sample of Na2Se was added in to a magnetically stirred
ice-cooled solution of 4 (1.19 g, 1.34 mmol, 1 equiv) in 50 mL acetone. The reaction
mixture was stirred over night at room temperature, and the precipitate was filtered off,
dried in vacuo, giving 2 as amorphous white solid (0.854 g, 0.938 mmol, 70 % yield). Due
to the sensibility of 2, a part of the product was oxidized to elemental Se under air). Further
purification was achieved by recrystallization from dichloromethane - diethyl ether to give
transparent needles with a mp of 280-286◦.
1H NMR (CDCl3, 600.29, 298 K): δ 0.36 (s, 3H, 4J(1H – 117/119Sn) = 10 Hz, 2J(1H – 29Si)
= 20 Hz, 5J(1H – 77Se) = 120 Hz, SiCH3), 0.90 (s, 6H, 2J(1H – 117/119Sn) = 72 Hz,
3J(1H – 77Se) = 122 Hz, SiCH2Sn), 7.42-7.72 (complex pattern, 15H, Ph). 13C{1H} NMR
(CDCl3, 150.94, 298 K): δ 5.23 (1J(13C – 29Si) = 52 Hz, 1J(13C – 117/119Sn) = 245/256 Hz,
SiCH2Sn), 9.37 (3J(13C – 117/119Sn) = 43 Hz, 1J(13C – 29Si) = 85 Hz, SiCH3), 128.91
(3J(13C – 117/119Sn) = 61 Hz, Cm), 130.07 (4J(13C – 117/119Sn) = 15 Hz, 5J(13C – 77Se) =
56 Hz, Cp), 134.50 (2J(13C – 117/119Sn) = 54 Hz, Co), 140.67 (3J(13C – 117Sn) = 10 Hz,
3J(13C – 77Se) = 52 Hz, 1J(13C – 117/119Sn) = 547/571 Hz, Ci). 29Si NMR (CDCl3, 119.26,
298 K): δ 13.88 (2J(29Si – 117/119Sn) = 41 Hz, 1J(29Si – 13C) = 87 Hz, CH2SiMe). 119Sn
NMR (CDCl3, 149.26, 298 K): δ 2.44 (2J(119Sn-115Sn) = 2442 Hz, 1J(119Sn – 77Se)
= 1231 Hz, 1J(119Sn – 13Ci) = 573 Hz, 2J(119Sn – 117Sn) = 217 Hz, SnPhSe). 77Se NMR
(CDCl3, 114.48, 298 K): δ –346.75 (1J(77Se – 117/119Sn) = 1168/1225 Hz, SeSnPh). Anal.
Calcd (%) for C22H24Se3SiSn3 + MeOH + 2H2O: C 28.26, H 3.3. Found: C 28.3, H 3.3.
Electrospray MS: (positive mode) m/z (%) 2163.07 {30, [MeSi(CH2SnPhO)3]3 + 2H+}2+.
• Synthesis of 7-Methyl-1,3,5-tris((trimethylsilyl)methyl)-2,4,9-trithio-7-sila-
1,3,5-tristannaadamantane: MeSi[CH2Sn(CH2SiMe3)S]3 (35)
A (0.643 g, 439.09 µmol, 1 equiv) sample of 11 was dissolved in 30 mL acetone and added
dropwise to a magnetically stirred ice-cooled solution of Na2S.9H2O (0.340 g, 1.41 mmol,
3.2 equiv) in water. The reaction mixture was stirred over night at room temperature, and
the precipitate was filtered off, dried in vacuo, giving 7a as amorphous white solid (0.343
g, 430.3 µmol, 98 % yield). Further purification was achieved by recrystallization from
acetone to give transparent needles with a mp of 190-196 ◦C.
1H NMR (CDCl3, 400.25, 298 K): δ 0.30 (s, 3H, 4J(1H – 117/119Sn) = 10 Hz, SiCH3),
0.15-0.17 (s, 27H, SiMe3), 0.55 (s, 6H, 2J(1H – 117/119Sn) = 87/92 Hz, SiCH2Sn), 0.47
(s, 6H, CH2SiMe3). 13C{1H} NMR (CDCl3, 150.94, 298 K): δ 1.39 (1J(13C – 29Si)
= 54 Hz, 3J(13C – 117/119Sn) = 23 Hz, SiMe3), 7.62 (1J(13C – 117/119Sn) = 260/273 Hz,
1J(13C – 29Si) = 50 Hz, SnCH2SiMe3), 9.03 (3J(13C – 117/119Sn) = 38 Hz, SiMe), 10.62
(1J(13C – 117/119Sn) = 287/300 Hz, 1J(13C – 29Si) = 42 Hz, SiCH2Sn). 29Si NMR (CDCl3,
119.26, 298 K): δ 2.26 (2J(29Si – 117/119Sn) = 30 Hz, 1J(29Si – 13C) = 56 Hz, (CH2SiMe3),
11.33 (2J(29Si – 117/119Sn) = 52 Hz, SnCH2SiMe). 119Sn NMR (CDCl3, 149.26, 298 K):
δ 152.7 (2J(119Sn – 117Sn) = 202 Hz, 2J(119Sn-115Sn) = 3625 Hz, SnCH2SiMe3S). Anal.
184
4. MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph , CH2SiMe3) as Precursors
for Unprecedented Diorganotin Oxo Clusters and Adamantane-like Structures
Calcd (%) for C16H42S3Si4Sn3: C 24.05, H 5.3. Found: C 24.2, H 5.3. Electrospray MS:
m/z (%) positive mode 798.8659 (100, [M + H+]+ ) [C16H43S3Si4Sn3]+).
• Redistribution reaction of 33 and 34 in CDCl3
A (0.0186 g, 24.19 µmol, 1 equiv) sample of pure 33 was dissolved in 5 mL CDCl3 and
added to (0.022 g, 24.19 µmol, 1 equiv) sample of pure 34. The reaction mixture was stirred
for 30 min and send to 119Sn NMR measurement. Series of 119Sn NMR measurements
were realized over a period of 78 Days to study the redistribution reactions taking place in
this reaction mixture.
119Sn NMR (CDCl3, 223.85, 298 K, Day 21): δ 2.9 ppm (SnSe2, A, 34), 0.3 ppm (SnSe2,
C, 1Sn), 52.6 ppm (SSnSe, C, 2Sn), 100.4 (SnS2, D, 1Sn), 50.5 (SSnSe, D, 2Sn), 98.9 ppm
(SnS2, B, 33). 77Se NMR (CDCl3, 114.48, 298 K): δ –346.7 ppm (SeSn, D, 1Se), -346.5
ppm (1J(77Se – 117/119Sn) = 1221/1163 Hz, SeSn, A, 3Se), -346.2 ppm (SeSn, C, 2Se).
• Redistribution reaction of 33 and 34 in C6D6
A (0.0186 g, 24.19 µmol, 1 equiv) sample of pure 33 was dissolved in 5 mL C6D6 and
added to (0.022 g, 24.19 µmol, 1 equiv) sample of pure 34. The reaction mixture was stirred
for 30 min and send to 119Sn NMR measurement. Series of 119Sn NMR measurements
were realized over a period of 39 Days to study the redistribution reactions taking place in
this reaction mixture.
119Sn NMR (CDCl3, 223.85, 298 K, Day 39): δ 2.59 ppm (SnSe2, A, 34), 0.23 ppm (SnSe2,
C, 1Sn), 53.06 ppm (SSnSe, C, 2Sn), 101.7 (SnS2, D, 1Sn), 50.95 (SSnSe, D, 2Sn), 100.1
ppm (SnS2, B, 33).
• Redistribution reaction of 34 and S8 in CDCl3
A (0.057 g, 62.67 µmol, 1 equiv) sample of pure 34 was dissolved in 5 mL CDCl3 and
added to (0.016 g, 62.67 µmol, 1 equiv) sample of S8. The reaction mixture was stirred for
30 min and send to 119Sn NMR measurement. Series of 119Sn NMR measurements were
realized over a period of 53 Days to study the redistribution reactions taking place in this
reaction mixture.
119Sn NMR (CDCl3, 149.26, 298 K, Day 7): δ 2.47 ppm (SnSe2, A, 34), 0.23 ppm (SnSe2,
C, 1Sn), 52.1 ppm (SSnSe, C, 2Sn), 100.17 (SnS2, D, 1Sn), 50.09 (SSnSe, D, 2Sn), 98.6
ppm (SnS2, B, 33).
185
5. The Unprecedented Octanuclear Organotin Oxo Clus-
ter {[MeSi(MeSnCl)(CH2)3(µ3 – O)(MeSnCl)(CH2)3]2O}2
5.1 Introduction
Controlled hydrolysis of diorganotin dichlorides gives dimeric tetraorganodistannoxanes
[R2XSnOSnXR’2]2 (X = Cl, OH) of type A (Scheme 37). There is an increased interest
of such compounds, given their applications as catalysts in organic chemistry and their
capacity to present a variety of molecular structures depending on the substituents bound
to the tin centres.[20] A special class of tetraorganodistannoxanes are compounds derived
from spacer-bridged ditin derivatives. These tetraorganodistannoxanes exhibit so-called
double ladder structures.
This chapter reports a novel such compound the central part of which contains a siloxane
moiety.
Scheme 37. Base hydrolysis as a Synthesis method for obtaining ladder-like tetraorgan-
distannoxanes.
Sn O
X
Sn X
Sn
X
OSnX
R'
R
R
R'
R'
R
R
R'
2 H2O/Base
-4 HX
R, R' = Alkyl, Aryl;  X = Halogen, OH, OC(O)R', OR', OSiR'3, NR'2, NCO, NCS,
4 R2SnX2
A
5.2 Synthesis and structure
The reaction under non-inert conditions of the organochlorosilane
MeClSi((CH2)3SnMeCl2)2, 1, with an excess of pyridine in CH3CN solution gives
a slightly yellow oily material that is soluble in CH3CN. Compound 1 was supplied from
the stock in the laboratory. No procedure for its synthesis was avialable. A 119Sn NMR of
this crude mixture, in CDCl3, (See Supporting Information, Chapter 5, Figure S1), shows
two major broad signals at δ –43 ppm (38 %) and 48 ppm (43 %), referring to the the
186
5. The Unprecedented Octanuclear Organotin Oxo Cluster
{[MeSi(MeSnCl)(CH2)3(µ3 – O)(MeSnCl)(CH2)3]2O}2
distannoxane derivative 2, four lower-intense signals at -132, -127, -84, and -76 ppm, with
a whole integration of 10 % to which no assignments are made, and one signal referring
to the remaining compound 1 at δ 162 ppm (4 %).
A crystalline material is isolated from this reaction mixture suit-
able for X-ray diffraction study, corresponding to compound 2,
{[MeSi(MeSnCl)(CH2)3(µ3 – O)(MeSnCl)(CH2)3]2O}2, (Scheme 38) as colourless
crystals suitable for X-ray diffraction study.
Scheme 38. Synthesis of the distannoxane derivative 2.
Si
Cl
Me
Sn
SnMe
Cl
Cl
Me
Cl
Cl Excess Pyridine/ H2O
CH2Cl24 SiMe
O
Sn
Sn
Me
Cl
Cl
Me
ClCl
Si
Me
Sn
Sn
Me
Me
Si
Me
Sn
Sn
Me
Me
SiO
Me
Sn
Sn
Me
Cl
Cl
Me
Cl
Cl
O
O
O
O
further unknown species
+
Figure 95 shows the molecular structure of 2. The figure caption contains selected inter-
atomic distances and angles. Compound 2 shows a centrosymmetric head-to-tail dimer pre-
senting a double ladder structure in which two planar Sn4Cl4O2 layers are linked by eight
silicon-containing trimethylene chains. The four silicon atoms form two siloxanes bridges.
This makes the structure unique given that it is the first octanuclear double ladder organotin
oxocluster containing siloxane moieties linked to the bridging alkyl chains, referring to the
Cambridge Structural Data Base.[60] This structure shows a similarity to the monomeric
ladder-like compound 27, {[MeSi(CH2)3]SnCl(CH2SiMe3)(µ3 – O)SnCl(CH2SiMe3)
Sn(µ3 – O)(Cl)2(CH2SiMe3)Sn(t-Bu)2} of Chapter 4 presenting a similar layer moiety.
The exocyclic Sn atoms in this latter are unsymmetrically substituted.
Compound 2 contains four crystallographical independent tin atoms (Sn1, Sn2, Sn3 and
Sn4) (Figure 94). The Sn(1) and Sn(2) atoms are incorporated in the central four-membered
Sn2O2-ring as for Sn(3) and Sn(4) are bonded exocyclic to this ring. The endocyclic
Sn atoms Sn(1) and Sn(2) are hexa-coordinated and exhibit each a distorted octahedral
all-trans SnC2Cl2O2 environment at with angles of (O1–Sn1–Cl1) 150.525(4)◦, (O2–Sn1–
Cl4) 138.64(5)◦, (Cl1–Sn1–Cl4) 143.496(3)◦, (O1–Sn1–C11) 96.497(6)◦, (O2–Sn1–C11)
187
5. The Unprecedented Octanuclear Organotin Oxo Cluster
{[MeSi(MeSnCl)(CH2)3(µ3 – O)(MeSnCl)(CH2)3]2O}2
123.003(7)◦, (C1–Sn1–C11) 129.872(13)◦, (O1–Sn2–Cl3) 136.386(5)◦, (O2–Sn2–Cl2)
150.871(4)◦, (Cl2–Sn2–Cl3) 144.507(3)◦, (O1–Sn2–C21) 109.794(7)◦, (O2–Sn2–C21)
100.474(7)◦, and (C2–Sn2–C21) 136.559(15)◦. The chlorido- and the oxido- bridges Cl–
Snendo–Cl and O–Snendo–O are unsymmetrical at Sn(2) and Sn(3) with Sn(1)–Cl(1), Sn(1)–
Cl(4), Sn(1)–O(1), Sn(1)–O(2), Sn(2)–Cl(2), Sn(2)–Cl(3), Sn(2)–O(1), Sn(2)–O(2), dis-
tances equal to 2.6699(5), 3.4646(5), 2.0387(3), 2.052(4), 2.7176(5), 3.3512(5), 2.027(4),
and 2.116(3) Å, respectively. The chlorine atoms Cl(3) and Cl(4) are approaching, respec-
tively, Sn(2) and Sn(1), and making the environment hexaccordinated, given that bond
distances (Sn1–Cl4) 3.4646(5) Å and (Sn2–Cl3) 3.3512(5) Å, are shorter than the sum of
van der Waals radii of tin (2.17 Å) and chlorine (1.75 Å).[30]
The exo-cyclic tin atoms Sn(3) and Sn(4) exhibit a distorted trigonal bipyramidal environ-
ments, with the equatorial positions being occupied by two carbon atoms and one oxygen
atom (C(3), C(31), O(2) for Sn(3)), (C(4), C(41), O(1) for Sn(4)).
As to the axial positions, are being occupied by two chlorine atoms (Cl1, Cl3 for Sn3, and
Cl2 and Cl4 for Sn4). The geometrical goodnes ∆Σ(θ)[22] is 62.6◦ for Sn(3) and 82.6◦
for Sn(4). The Snexo–O interatomic distances range between 2.0361(3) and 2.1192(4) Å,
corresponding to Sn(3)–O(2) and Sn(4)–O(1), respectively, which are longer than the
Snendo–O bond distances. The Cl–Snexo–Cl bridges are unsymmetrical with distances of
Sn(3)–Cl(1) 2.817(5) Å, Sn(3)–Cl(3) 2.4553(4) Å, Sn(4)–Cl(2) 2.7349(5) Å, and Sn(4)–
Cl(4) 2.492(4) Å.
Bond distances and angles around the siloxane-bridges are similar to the correspond-
ing bridges in siloxane-containing compounds reported in the literature.[22] The Si–O
intramolecular distances are equal to 1.5966(3) and 1.6736(3) Å, corresponding, respec-
tively, to Si(1)–O(3) and Si(2)–O(3). The corresponding angle is equal to 151.168(8)◦
(Si1–O3–Si2).
188
5. The Unprecedented Octanuclear Organotin Oxo Cluster
{[MeSi(MeSnCl)(CH2)3(µ3 – O)(MeSnCl)(CH2)3]2O}2
189
5. The Unprecedented Octanuclear Organotin Oxo Cluster
{[MeSi(MeSnCl)(CH2)3(µ3 – O)(MeSnCl)(CH2)3]2O}2
Figure 95. POV-Ray image of the molecular structure of
{[MeSi(CH2)3]SnCl(CH2SiMe3)(µ3-O)SnCl(CH2SiMe3)Sn(µ3-O)(Cl)2 (CH2SiMe3)
Sn(Me)2}, 2. Selected interatomic distances (Å): Sn(1)–Cl(1) 2.6699(5), Sn(1)–Cl(4)
3.4646(5), Sn(1)–O(1) 2.0387(3), Sn(1)–O(2) 2.052(4), Sn(2)–Cl(2) 2.7176(5), Sn(2)–
Cl(3) 3.3512(5), Sn(2)–O(1) 2.027(4), Sn(2)–O(2) 2.116(3), Sn(1)–Cl(4) 3.4646(5),
Sn(2)–Cl(3) 3.3512(5), Si(1)–O(3) 1.5966(3), Si(2)–O(3) 1.6736(3) Selected interatomic
angles (◦): O(1)–Sn(1)–Cl(1) 150.525(4), O(2)–Sn(1)–Cl(4) 138.64(5), Cl(1)–Sn(1)–Cl(4)
143.496(3), O(1)–Sn(1)–C(11) 96.497(6), O(2)–Sn(1)–C1(1) 123.003(7), C(1)–Sn(1)–
C(11) 129.872(13), O(1)–Sn(2)–Cl(3) 136.386(5), O(2)–Sn(2)–Cl(2) 150.871(4),
Cl(2)–Sn(2)–Cl(3) 144.507(3), O(1)–Sn(2)–C(21) 109.794(7), O(2)–Sn(2)–C(21)
100.474(7), C(2)–Sn(2)–C(21) 136.559(15), O(2)–Sn(3)–C(3) 109.535(5), Cl(1)–
Sn(3)–Cl(3) 161.41(5), O(1)–Sn(4)–C(4) 106.725(6), Cl(2)–Sn(4)–Cl(4) 165.356(5),
Si(1)–O(3)–Si(2) 151.168(8).
Giving the lack of material, no further investigation in solution was done. An ESI-
MS spectrum (positive mode) of 2 shows low intense mass clusters centred at m/z
1228.7775 and 1923.5218 corresponding, respectively, to the cations [C26H68ClOSi3Sn6]+
and [C35H94Cl8O3Si4Sn8]+ (See Supporting Information, Chapter 5, Figures S2-S5).
5.3 Conclusion
Compound 2 presents a new type of double ladder-like structure, preserving the structural
moeity characteristic of tetraoganodistannoxanes and presenting siloxanes bridging in the
skeleton. Within the time frame of this PhD, no further studies of its behaviour in solution,
could be performed. However, such compound holds potential for novel generation of its
own.
5.4 Experimental section
• Synthesis of {[MeSi(MeSnCl)(CH2)3(µ3 – O)(MeSnCl)(CH2)3]2O}2 (2)
To a solution of MeClSi((CH2)3SnMeCl2)2, 1, (109.00 mg, 0.19 mmol) in 15 mL of
CH3CN was added three molar equiv of pyridine (45.2 mg, 0.57 mmol). The resulting
mixture was stirred at room temperature overnight. A crystalline material of 2 is isolated
as colourless crystals from this reaction mixture (10 mg, 11 % yield).
Anal. Calcd (%) for C36H88Cl8O6Si4Sn8 + 2 pyridine + CH3CN: C 26.7, H 4.7, N 1.94.
Found: C 26.0, H 4.5, N 2.2. Electrospray MS: m/z (%) positive mode: 1228.7775
[C26H68ClOSi3Sn6]+ and 1923.5218 [C35H94Cl8O3Si4Sn8]+.
190
6. Novel Triorganotin-functionalized Aminoalcohol
Derivatives as Potential Precursors for the Synthesis
of Organtin-containing Azidocryptands
6.1 Introduction
Since the innovative works from Pedersen, Lehn, and Cram work[61,62] on crown-ethers,
cryptands, and related species, host-guest supramolecular chemistry became the focus of
research,[62] The concept got new momentum when by combining crown ethers with Lewis
acids thus creating so-called ditopic receptors that bind cations and anions simultaneously.
One representative is the complex A (Scheme 39) in which sodium fluoride, NaF, is
ditopically complexed by such a host.
Scheme 39. Ditopic complex of sodium fluoride, NaF.[63]
O
O
O
Sn
Ph
I
O
O
Na
Sn
I
F
Ph
Ph
O
CH3
H
A challenge for future work is to synthesize a host combined of a cryptand and a Lewis
acid, as it is shown in Scheme 40. This short chapter reports preliminary results on the
way to achieve this goal.
191
6. Novel Triorganotin-functionalized Aminoalcohol Derivatives as Potential Precursors
for the Synthesis of Organtin-containing Azidocryptands
Scheme 40. Concept of synthesis of organotin-functionalized cryptand.
Sn
Ph
Ph Ph
NH2
+
O
Sn
Ph
Ph Ph
N OH
OHexcess
1 2
120°C
2PPh3/ 2 CCl4 −2 Ph3PO/ −2 CHCl3
Sn
Ph
Ph Ph
N Cl
Cl
A O
N
O O
O
N HH+
M
O
N
O O
O
N
N
X
M+
 
=
 
K+, X = (CH2)2SnPh3
−2 HCl
6.2 Synthesis of Ph3Sn(CH2)2N[CH2C(CH3)2OH]2 and
its reaction with tetra-tert-butoxystannane
The reaction of a slight excess of 2-chloroethyl amine, obtained via reaction between
equimolar amounts of trimethylamine and 2-chloroethylamine hydrochloride,[64] with one
molar equiv of sodium triphenylstannide, NaSnPh3, in THF affords a white solid mate-
rial that is soluble in almost all organic solvent. A 119Sn NMR spectrum of a solution
of this material, in C6D6, (Figure 96), shows one resonance at δ -100 ppm. Recrystal-
lization from diethyl-ether/ dichloromethane affords 1-triphenylstannyl-2-aminoethane,
Ph3Sn(CH2)2NH2, 1, as colourless crystals suitable for X-ray diffraction analysis (Scheme
41).
192
6. Novel Triorganotin-functionalized Aminoalcohol Derivatives as Potential Precursors
for the Synthesis of Organtin-containing Azidocryptands
Figure 96. 119Sn NMR spectrum (149.26 MHz, C6D6) of crude mixture reaction of com-
pound 1.
Scheme 41. Synthesis of Ph3Sn(CH2)2NH2, 1.
Compound 1 crystallizes in the monoclinic space group P21/n, with two molecules in the
unit cell.
Figure 97 shows the molecular structure of 1, and the figure caption contains selected
interatomic distances and angles.
193
6. Novel Triorganotin-functionalized Aminoalcohol Derivatives as Potential Precursors
for the Synthesis of Organtin-containing Azidocryptands
Figure 97. POV-Ray image of the molecular structure of Ph3Sn(CH2)2NH2, 1. Hydrogens
are omitted for clarity. Selected interatomic distances (Å): Sn(1)–N(1) 3.049(3), Sn(1)–
C(21) 2.136(3), Sn(1)–C(31) 2.159(3). Selected interatomic angles (◦): C(3)–Sn(1)–N(1)
52.08(10), C(11)–Sn(1)–N(1) 83.93(9), C(21)–Sn(1)–N(1) 87.78(9), C(31)–Sn(1)–N(1)
157.13(9), C(11)–Sn(1)–C(3) 114.19(11), C(21)–Sn(1)–C(3) 113.74(11), C(31)–Sn(1)–
C(3) 105.07(10), C(11)–Sn(1)–C(21) 109.63(10), C(11)–Sn(1)–C(31) 108.50(10), C(21)–
Sn(1)–C(31) 105.09(10).
The Sn(1) atom is pentacoordinated and exhibits a distorted trigonal bipyramidal environ-
ment, with N(1), and C(31) occupying the axial, and C(3), C(11), and C(21) occupying
the equatorial positions. The geometrical goodness ∆Σ(θ)[22] is equal to 18.9◦. There is a
rapprochement of N(1) to the Sn centre via NSn intramolecular coordination equal to
3.049(3) Å (Sn1–N1), which is shorter than the sum of van der Waals radii of Sn (2.27 Å)
and N (1.55 Å). This bond distance is longer than those corresponding in comparable com-
pounds such as {Me2N(CH2)3}Ph3SnCH2,[29] in which Sn–N is equal to 2.433(3) Å and
in [Me2NCH2N(CH2CH2O)2]2Sn, in which Sn–N is equal to 2.524(2) Å.[65] The Sn–C
vary between 2.136(3) Å (Sn1–C21) and 2.159(3) Å (Sn1–C31).
194
6. Novel Triorganotin-functionalized Aminoalcohol Derivatives as Potential Precursors
for the Synthesis of Organtin-containing Azidocryptands
A 119Sn NMR spectrum of a crystalline material of compound 1 dissolved in in CDCl3
shows one singlet resonance at -102 ppm (1J(119Sn – 13Ci) = 490 Hz). A 1H NMR spec-
trum shows the singlet corresponding to the NH2 protons at δ 1.81 ppm and the triplet
resonances assigned to the (CH2Sn) protons at δ 1.92 ppm (2J(1H – 117/119Sn) = 60 Hz) and
to the (CH2N) protons at δ 3.26 ppm (3J(1H – 117/119Sn) = 40 Hz). The complex pattern
referring to the protons of the phenyl groups appears at δ 7.32– 8.01 ppm with integra-
tion of 15H. In a 13C NMR spectrum (C6D6 solution), the chemical shift at δ 17.41 ppm
(1J(13C – 117/119Sn) = 385/404 Hz) is assigned to the (CH2Sn) carbon atom (C3) and at δ
38.8 ppm is assigned to the (CH2N) carbon atom (C2). (Figure 97)
An electrospray ionization mass spectrum (ESI MS positive mode) shows an intense
mass cluster centred at m/z 344.04 corresponding to the anion [C14H16NaSn]+. An IR
spectrum shows an absorption band at ν 3100 cm−1, corresponding to the NH2 group (See
Supporting Information, Chapter 6, Figures S1- S6).
Heating of an excess of isobutylene oxide with one molar equiv of 1 in a pressure Young-
vessel during three days, affords a yellow oily substance soluble in almost all organic
solvent. After removal of volatiles at reduced pressure and recrystallization from diethyl-
ether/dichloromethane affords bis-triphenylstannylethylenamine(2-methyl-2-propanol),
Ph3Sn(CH2)2NH2(CH2CMe2OH)2, 2, as colourless crystals suitable for X-ray diffraction
analysis (Scheme 42).
Scheme 42. Synthesis of Ph3Sn(CH2)2NH2(CH2CMe2OH)2, 2.
Sn
Ph
Ph Ph
NH2
+
O
Sn
Ph
Ph Ph
N OH
OHexcess
1 2
120°C
3 d
Compound 2 crystallizes in the monoclinic space group P21/n with two molecules in the
unit cell. Figure 98 shows the molecular structure of 2 and the figure caption contains
selected interatomic distances and angles.
195
6. Novel Triorganotin-functionalized Aminoalcohol Derivatives as Potential Precursors
for the Synthesis of Organtin-containing Azidocryptands
Figure 98. POV-Ray image of the molecular structure of
Ph3Sn(CH2)2NH2(CH2CMe2OH)2, 2. Hydrogens are omitted for clarity. Selected
interatomic distances (Å): H(11)–O(21) 1.984, Sn(1)–C(41) 1.990(3), Sn(1)–C(51)
2.342(4). Selected interatomic angles (◦): C(3)–Sn(1)–C(31) 109.8(4), C(3)–Sn(1)–C(41)
110.6(4), C(3)–Sn(1)–C(51) 115.3(4), C(31)–Sn(1)–C(51) 104.07(18), C(31)–Sn(1)–C(41)
110.6(2), C(41)–Sn(1)–C(51) 106.31(19), C(2)–N(1)–C(12) 112.3(11), C(2)–N(1)–C(22)
112.0(12), C(12)–N(1)–C(22) 113.2(14).
The Sn(1) atom exhibits a tetrahedral environment, with angles varying between
104.07(18)◦ (C31–Sn1–C51) and 109.8(4)◦ (C3–Sn1–C31). The Sn–C distances vary be-
tween 1.990(3) Å (Sn1–C41) and 2.342(4) Å (Sn1–C51). The C–N–C angles are almost
equal, varying between 112.0(12)◦ (C22–N1–C2) and 113.2(14)◦ (C22–N1–C12). There
is a hydrogen bond O(11) –H(11) · · · O(21) at a O(11)–O(21) distance of 1.984 Å.
A 119Sn NMR spectrum of a crystalline material of compound 2 in CDCl3 shows one
singlet resonance at –129 ppm. A 1H NMR spectrum shows the singlet corresponding to
the CH3 protons at 1.18 ppm. The signal for the OH protons appears at δ 1.36 ppm, the
multiplet resonances assigned to the (CH2Sn) protons appear at δ 1.71 and to the (CH2N)
protons at 2.98 ppm. As to the resonance corresponding to the CCH2 protons appears at
2.63 ppm. The complex pattern referring to the phenyl protons appears at δ 7.39- 7.70
ppm with integration of 15H. In a 13C NMR spectrum (CDCl3 solution), the chemical
196
6. Novel Triorganotin-functionalized Aminoalcohol Derivatives as Potential Precursors
for the Synthesis of Organtin-containing Azidocryptands
shifts at δ 8.31 and 56.3 ppm are assigned to the (CH2Sn) carbon atom (C3) and the
(CH2N) carbon atom (C2), respectively (Figure 98). In the aromatic part, the chemical
shifts corresponding to the carbon atoms Cm) at δ 128.56 ppm (3J(13C – 117/119Sn) =
46 Hz) ppm, Cp) at δ 129.01 ppm (4J(13C – 117/119Sn) = 15 Hz), Co at δ 136.0 ppm, and Ci
at δ 138.03 ppm (1J(13C – 117/119Sn) = 500 Hz). An electrospray ionization mass spectrum
(ESI MS positive mode) shows mass clusters centred at m/z 540.2 corresponding to the
cation [M + H+]+). An IR spectrum reveals an absorption band at ν 3500-2966 cm−1,
corresponding to OH groups (See Supporting Information, Chapter 6, Figures S9- S15).
The reaction mixture of two molar equiv of 2 with one molar equiv of (t– BuO)4Sn in
toluene is heated at reflux over night to afford a slightly yellow oily substance soluble in
almost all organic solvent. Recrystallization from toluene affords the spiro-type compound
spiro-[Ph3Sn(CH2)2NH2(CH2CMe2O)2]2Sn, 3, as colourless crystals suitable for X-ray
diffraction analysis (Scheme 43).
Scheme 43. Synthesis of [Ph3Sn(CH2)2NH2(CH2CMe2O)2]2Sn, 3.
+
Sn
Ph
PhPh
NO
O
2 Sn
O
O
Sn
Ph
Ph
Ph
N + t-BuOH4Sn
Ph
Ph Ph
N OH
OH
2
(t-BuO)4Sn
Toluene, reflux
3
Compound 3 crystallizes in the triclinic space group P–1 group with two molecules in the
unit cell.
Figure 99 shows the molecular structure of 3 and the figure caption contains selected
interatomic distances and angles.
197
6. Novel Triorganotin-functionalized Aminoalcohol Derivatives as Potential Precursors
for the Synthesis of Organtin-containing Azidocryptands
Figure 99. POV-Ray images of the molecular structure of
[Ph3Sn(CH2)2NH2(CH2CMe2O)2]2Sn, 3; left: complete presentation of the molec-
ular structure of 3 (only hydrogens are omitted for clarity), right: Simplified presentation
with only Ci of the phenyl groups are presented and hydrogens are omitted for clarity.
Selected interatomic distances (Å): Sn(1)–O(1) 2.0051(14), Sn(1)–O(2) 1.9969(14),
Sn(1)–O(3) 1.9941(15), Sn(1)–O(4) 1.9936(15), Sn(1)–N(1) 2.4439(17), Sn(1)–N(2)
2.3699(17). Selected interatomic angles (◦): O(1)–Sn(1)–O(2) 110.32(6), O(1)–Sn(1)–
O(3) 102.41(6), O(1)–Sn(1)–O(4) 135.65(7), O(2)–Sn(1)–O(3) 85.75(6), O(2)–Sn(1)–O(4)
102.16(6), O(3)–Sn(1)–O(4) 109.46(6), O(1)–Sn(1)–N(1) 77.45(6), O(1)–Sn(1)–N(2)
82.38(6), O(2)–Sn(1)–N(1) 76.67(6), O(2)–Sn(1)–N(2) 159.53(6), N(2)–Sn(1)–N(1)
122.79(6), O(3)–Sn(1)–N(1) 160.97(6), O(3)–Sn(1)–N(2) 75.62(6), C(11)–Sn(2)–C(23)
105.60(9), C(39)–Sn(3)–C(51) 112.83(9), C(2)–N(1)–C(9) 110.86(16), C(34)–N(2)–C(37)
114.23(17).
The Sn(1) atom is hexa-coordinated and exhibits a distorted octahedral SnO4N2 environ-
ment. The N(1) and N(2) atoms coordinate the Sn(1) centre in cis position at distances
of 2.4439(17) Å (Sn1–N1) and 2.3699(17) Å (Sn1–N2), respectively. These distances are
shorter than the sum of van der Waals radii of Sn (2.27 Å) and N (1.55 Å).[29] These bond
distances are comparable to the corresponding in [MeN(CH2CH2CH2O)2]2Sn,[66] with
Sn–N ranging between 2.285(3) and 2.381(3) Å, and shorter than those corresponding in
comparable compounds such as in [Me2NCH2N(CH2CH2O)2]2Sn, in which Sn–N is equal
to 2.524(2) Å[66] and in [MeOCH2N(CH2CH2O)2]2Sn with the corresponding Sn–N bond
is equal to 2.526(2) Å,[65] and the resembling stannylene compound RN(CH2CR’2O)2 Sn;
R = CH2CMe2OH, R’ = H,[66] in which Sn–N is equal to 2.561(3) Å. There are four OSn
intramolecular coordination with bond distances of 2.0051(14), 1.9969(14), 1.9941(15),
and 1.9936(15), corresponding to Sn(1)–O(1), Sn(1)–O(2), Sn(1)–O(3), and Sn(1)–O(4),
198
6. Novel Triorganotin-functionalized Aminoalcohol Derivatives as Potential Precursors
for the Synthesis of Organtin-containing Azidocryptands
respectively. These later are all shorter than the corresponding Sn-O bond distances in the
spiro-type compounds [Me2NCH2N(CH2CH2O)2]2Sn and [MeOCH2N(CH2CH2O)2]2Sn,
with Sn–O, respectively, of 2.130(2)/ 2.253(2), and 2.128(2)/ 2.250(2) Å.[65] The O–
Sn–O angles O(1)–Sn(1)–O(2), O(1)–Sn(1)–O(3), O(1)–Sn(1)–O(4), O(2)–Sn(1)–O(3),
O(2)–Sn(1)–O(4), and O(3)–Sn(1)–O(4) are equal to 110.32(6), 102.41(6), 135.65(7),
85.75(6), 102.16(6), and 109.46(6)◦, respectively. These angles are comparable to
those corresponding in [Me2NCH2N(CH2CH2O)2]2Sn,[65] varying between 69.09(7)◦and
100.50(7)◦, [MeOCH2N(CH2CH2O)2]2Sn,[65] varying between 68.50(7)◦and 101.69(8)◦
and smaller than those corresponding in [MeN(CH2CH2CH2O)2]2Sn,[66] varying between
92.33(10)◦and 154.12(10)◦. The O–Sn–N angles vary between 75.62(6)◦ (O3–Sn1–N2)
and 160.97(6)◦ (O3–Sn1–N1). These values are comparable to those corresponding in
[MeN(CH2CH2CH2O)2]2Sn,[66] varying between 77.76(10)◦and 165.89(10)◦.
The Sn(2) and Sn(3) atoms exhibit tetrahedral environment, with angles varying between
105.60(9)◦ (C23–Sn2–C11) and 112.83(9)◦ (C39–Sn3–C51). The C–N–C angles are com-
parable, varying between 110.86(16)◦ (C2–N1–C9) and 114.23(17)◦ (C34–N2–C37).
A 119Sn NMR spectrum of compound 3 in C6D6 shows two singlet resonances at δ –99
ppm (4J(119Sn – 117/119Sn) = 17 Hz) and δ –435 ppm (4J(119Sn – 117/119Sn) = 17 Hz) with
an integration of 2:1 respectively. The latter chemical shift is very close to the correspond-
ing Sn atom in [MeN(CH2CH2CH2O)2]2Sn,[66] at δ –449 ppm.
The 1H NMR spectrum shows the multiplet resonances assigned to the (CH2Sn) protons
at δ 0.75 ppm and (CH2N) protons at δ 3.26 ppm. The CH3 protons of the alkanol groups
appear at δ 1.17– 1.27 ppm. The resonance corresponding to (CH2N) protons of the
alkanol groups appear at 2.61 ppm (3J(1H – 117/119Sn1) = 233 Hz).
The complex pattern referring to the protons of the phenyl groups appears at δ 7.33–
7.58 ppm with integration of 30H. An electrospray ionization mass spectrum (ESI MS
positive mode) shows two mass clusters centred at m/z 538.4 and 562.4 corresponding,
respectively, to the cations [C28H37NO2Sn]+ and [C28H37NaNO2Sn]+ (See Supporting
Information, Chapter 6, Figures S16- S21).
6.3 Conclusion
Within the time frame of this PhD, further work could not be realized. However,
there is a promising start to achieve the main goal of this work which is function-
alization of the triorganotin-functionalized cryptand, based on the synthesized alkanol
amine organotin compound 2, bis-triphenylstannylethylenamine(2-methyl-2-propanol),
Ph3Sn(CH2)2NH2(CH2CMe2OH)2. This result is motivating in context with previous
work in our research group on of aminoalkanol derivatives of tin. It holds potential to
obtain polyfunctional ligands, applied for the synthesis of a new generation of functional
material in fields of catalysts and metal-organic frameworks...[65,66]
199
6. Novel Triorganotin-functionalized Aminoalcohol Derivatives as Potential Precursors
for the Synthesis of Organtin-containing Azidocryptands
6.4 Experimental section
• Synthesis of Ph3Sn(CH2)2NH2 (1)
To a solution of SnPh3Cl (10 g, 25.64 mmol) in THF (250 mL) were added a slight
excess of metallic sodium (1.25 g, 54.22 mmol) and a catalytic amount of naphtha-
lene. The mixture was stirred at room temperature for 3 days, during which its colour
changed to deep black. After the solution had been separated from non-reacted sodium,
2-chloroethylamine[65] (2.94 g, 36.97 mmol) was added dropwise at −70 ◦C under mag-
netic stirring. Overnight, the reaction mixture was warmed to room temperature and the
solvent was evaporated in vacuo. The residue obtained was extracted with 300 mL diethyl
ether followed by washing with 150 mL distilled water in order to remove the sodium
chloride. The organic phase was dried over anhydrous MgSO4 and filtrated. The solvent
was removed from the filtrate under reduced pressure, giving 1 as amorphous white solid
(9.22 g, 23.39 mmol, 95 % yield). Further purification was achieved by recrystallization
from diethyl-ether/ dichloromethane to give transparent needles with a mp of 76 ◦C.
1H NMR (CDCl3, 400.25, 298 K): δ 1.81 ppm (s, 2H, NH2), 1.92 ppm (t, 2H,
2J(1H – 117/119Sn) = 60 Hz, CH2Sn), 3.26 ppm (t, 2H, 3J(1H – 117/119Sn) = 40 Hz, CH2N),
7.32- 8.01 ppm (complex pattern, 15H, Ph). 13C {1H} NMR (C6D6, 100.64, 298 K): δ
17.41 ppm (1J(13C – 117/119Sn) = 385/404 Hz, CH2Sn), 38.8 ppm (CH2N), 128.35 ppm
(Cm), 129.09 ppm (4J(13C – 117/119Sn) = 11 Hz, Cp), 137.93 ppm (Co), 140.1 ppm (Ci).
119Sn NMR (C6D6, 149.26, 298 K): δ –102 ppm (1J(119Sn – 13C) = 490 Hz, SnPh3). Anal.
Calcd (%) for C20H21NSn: C 60.95, H 5.37, N 3.55. Found: C 60.0, H 5.4, N 3.5. Elec-
trospray MS: m/z (%) positive mode: 344.04 [100, C14H16NaSn+]+. IR (cm-1): ν(NH2)
3100 cm−1.
• Synthesis of Ph3Sn(CH2)2NH2(CH2CMe2OH)2 (2)
2-amino-ethyltriphenylstannane (1) (0.596 g, 1.51 mmol) and excess of isobutylene oxide
(1.09 g, 15.12 mmol) were placed in a glass vessel with a Young® valve, the mixture
was heated at 120 ◦C for three days, and the excess of isobutylene oxide was removed in
vacuum. Compound 2 was obtained as a yellow oily substance with a quantitative yield
(0.773 g, 1.43 mmol, 95 %). Recrystallization from diethyl-ether/ dichloromethane gave 2
as transparent needles.
1H NMR (CDCl3, 400.25, 298 K): δ 1.18 ppm (s, 12H, CH3), 1.36 ppm (s, 2H, OH), 1.71
ppm (m, 2H, CH2Sn), 2.63 (s, 4H, CH2CMe2), 2.98 ppm (m, 2H, , CH2N), 7.39- 7.70 ppm
(complex pattern, 15H, Ph). 13C {1H} NMR (CDCl3, 100.64, 298 K): δ 8.31 ppm (CH2Sn),
56.3 ppm (CH2N), 67.1 (CMe2CH2N), 71.21 (CMe2), 128.56 ppm (3J(13C – 117/119Sn) =
46 Hz, Cm), 129.01 ppm (4J(13C – 117/119Sn) = 15 Hz, Cp), 136.0 ppm (Co), 138.03ppm
(1J(13C – 117/119Sn) = 500 Hz, Ci). 119Sn NMR (CDCl3, 149.26, 298 K): δ –129 ppm
(SnPh3). Anal. Calcd (%) for C28H37NO2Sn: C 62.47, H 6.93, N 2.6. Found: C 62.5, H
200
6. Novel Triorganotin-functionalized Aminoalcohol Derivatives as Potential Precursors
for the Synthesis of Organtin-containing Azidocryptands
6.9, N 2.4. Electrospray MS: m/z (%) positive mode: 540.2 [C28H38NO2Sn]+: [M + H+]+.
IR (cm−1): ν(OH) 3500-2966 cm−1.
• Synthesis of [Ph3Sn(CH2)2NH2(CH2CMe2O)2]2Sn (3)
A solution of 2 (1.02, 1.89 mmol) in toluene (50 mL) was added to tetra-(tert-butyl ox-
ide)stannane (0.446 g, 0.947 mmol), and heated to reflux overnight. Solvent was removed
in vacuum. Compound 3 was obtained as white solid with very good yield (1.096 g, 0.916
mmol, 97 %). Recrystallization from toluene gave 3 colourless crystals with mp of 192.8-
194.4 ◦C.
1H NMR (CDCl3, 600.29, 298 K): δ 0.75 (m, 4H, CH2Sn), 1.17- 1.27 ppm (s, 24H, CH3),
2.61 ppm (s, 3J(1H – 117/119Sn1) = 233 Hz, 8H, CH2CMe2), 3.26 ppm (m, 4H, CH2N), 7.33-
7.58 ppm (complex pattern, 30H, Ph). 119Sn NMR (C6D6, 149.26, 298 K): δ –99 ppm
(4J(119Sn – 117/119Sn) = 17 Hz, 2Sn, SnPh3), -435 ppm (4J(119Sn – 117/119Sn) = 17 Hz, 1Sn,
SnO4). Anal. Calcd (%) for C56H74N2O4Sn3: C 56.27, H 6.24, N 2.34. Found: C 55.8,
H 6.0, N 2.2. Electrospray MS: m/z (%) positive mode: 538.4 [C28H37NO2Sn]+, 562.4
[C28H37NaNO2Sn]+.
201
7. Summary
The principal axes of this thesis project are the synthesis of tripodal
tris(organostannylmethyl)silanes of the type MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X
= I, F, Cl, Br; R = Ph, CH2SiMe3) , as building blocks for the synthesis of novel
organostannate complexes and umprecedented organotin chlacogeno-clusters among
which novel triangular belt-shaped diorganotin oxo clusters [MeSi(CH2SnRO)3]n, R
= Ph, CH2SiMe3 with gigantic nuclearity; oktokaideka (n = 18) and trikonta (n = 30).
Furthermore, formation of new spacer-bridged tetrastannanes R'Sn(CH2SnR(3 –n)Xn)3, (n
= 0– 2; X = I, Cl; R = Ph, R'= R, X) and their attempts for complexation are reported.
Moreover, there is synthesis of an unusual silicon-trimethylen-bridged double ladder
organotin oxo cluster. Finally, new aminoalkanol-triorganostannane derivatives as
precursors to build future tin-functionalized azidocryptands are reported. The numbering
of compounds are only related in chapters 2 and 4, and independent in chapters 3 and 5- 6.
The DVD contains Supporting Information of chapters 2- 6.
In the second chapter, there is report of a series of novel silicon-bridged organotin com-
pounds MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3), 2–
12, their syntheses and characterization (Chart 3), in addition to the study of complex-
ation behaviour of compounds 4-7, 9, and 12 with neutral and charged Lewis-base; Cl– ,
CH3COO– , F– , Br– , and HMPA (Chart 4. a, b).
202
7. Summary
Chart 3. The organotin compounds MeSi(CH2SnR(3 –n) Xn)3, 2– 12.
Si
Me
Sn
Sn
Sn
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Si
Me
Sn
Sn
Sn
I
Ph
Ph
Ph
Ph
I
Ph
Ph
I
3 I2,
CH2Cl2
−3 PhI
Si
Me
Sn
Sn
Sn
I
I
Ph
Ph
I
I
Ph
I
I
− 6 PhI
Si
Me
Sn
Sn
Sn
Br
Br
Br
Br
Br
Br
Br
Br
Br
9 Br2,
CH2Cl2
−9 PhBr
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
Si
Me
Sn
Sn
Sn
F
Ph
Ph
Ph
Ph
F
Ph
Ph
F
3 KF,
CH2Cl2/H2O
−3KI
6 AgCl,
CH2Cl2
−6 AgI
6 I2,
CH2Cl2
Si
Me
Sn
Sn
Sn
Br
Br
Ph
Br
Br
Ph
Ph
Br
Br
6 Br2,
CH2Cl2
−6 PhBr
Si
Me
Sn
Sn
Sn
Cl
Ph
Ph
Ph
Ph
Cl
Ph
Ph
Cl
3 AgCl,
CH2Cl2
−3 AgI
3 Me3SiCH2Cl
THF, 55−70°Χ
3 MgClI
C2H4Br2
+Si
Me
Sn
Sn
Sn
CH2SiMe3
Ph
Ph
CH2SiMe3
Ph
Ph
CH2SiMe3
Ph
Ph
3 Mg
Si
Me
Sn
Sn
Sn
CH2SiMe3
I
I
CH2SiMe3 I
I
CH2SiMe3
I
I
6 I2,
CH2Cl2, 0°C
−6 PhI
Si
Me
Sn
Sn
Sn
CH2SiMe3
Cl
Cl
CH2SiMe3
Cl
Cl
CH2SiMe3
Cl
Cl
6 AgCl,
CH2Cl2
−6 AgI
MeSi(CH2Cl)3 + 3 NaSnPh3
THF, −70°Χ −3 NaCl
1
2
3 4
5
6 7
8
9
1011
12
203
7. Summary
Chart 4 a). The organostannate complexes 13– 19.
Si
Me
Sn
Sn
Sn
O
O
Ph
Ph
Ph
Ph
O
O
O
Ph
O
Ph
Si Me
Sn
Sn
Sn
O
O
Ph
Ph
Ph
Ph
O
O
O
Ph
O
Ph
Si
Me
Sn
Sn
Sn
I
Ph
Ph
Ph
Ph
I
Ph
Ph
I
6 AgCH3COO,
CH2Cl2
−6 AgI
2
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
4
5
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph Cl
Cl
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
2 C11H21N2Cl, 
CH2Cl2
3 C11H21N2Cl, 
CH2Cl2
C11H21N2 2
C11H21N2 3
Cl
Cl
Cl
Cl Cl
P
O
N
NN
P
O
N
N
N
P
O
NN
N
6 HMPA, 
CH2Cl2
13
14
16
17
Si
Me
Sn
Sn
Sn
Cl
Ph
Ph
Ph
Ph
Cl
Ph
Ph
Cl
6
Si
Me
Sn
Sn
SnPh
Cl
Ph
Ph
Ph
Ph
Ph
P
O
N
N
N
18
P
O
N
N
N
Cl
Cl
Si
Me
Sn
Sn
Sn
Cl
Ph
Ph
Ph
Cl
Ph
Ph
Ph
Cl
P
O
N
NN
P
O
N
N
N
P
O
NN
N
19
· HMPA
+
4 HMPA, 
CH2Cl2
3 HMPA, 
CH2Cl2
Si
Me
Sn
Sn
Sn
Ph
Cl
Cl
Ph
Cl
Cl
Ph
Cl
Cl
NO3
 NO3PPh4, 
CH2Cl2
15
Si
Me
Sn
Sn
Sn
Ph
Cl Ph
Ph
Ph
Ph
Ph
P
O
N
N
N
P
O
N
N
N
Cl
Cl
+
(1)
(2)
PPh4
Chart 4 b). The organostannate complexes 20– 25.
In the third chapter, synthesis and characterization of R'Sn(CH2SnR(3 –n)Xn)3, (n = 0–
2; X = I, Cl; R = Ph, R'= R, X) derivatives are reported, and complexation attempts
of derivative ClSn(CH2SnPhCl2)3, 3, with chloride anion give interesting binuclear and
trinuclear organostannates 6– 9 (Chart 5).
204
7. Summary
Chart 5. R'Sn(CH2SnR(3 –n)Xn)3 derivatives 2– 5 and organostannate complexes 6– 9.
Sn
I
Sn
Sn
Sn
I
Ph
Ph
Ph
Ph
I
Ph
Ph
I
   4 I2,
CH2Cl2
− 4 PhI
Sn
Cl
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
7.5 HCl,
Diethyl ether
− 7 PhCl
Ph
Sn
Ph
Ph
Br Sn
Ph
Cl
Cl
Cl
+3 Sn
Ph
Sn
Sn
Sn
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
− 3 MgClBr
3.5 Mg,
THF, 75°C
Sn
Cl
Sn
Sn
Sn
Cl
Ph
Ph
Ph
Ph
Cl
Ph
Ph
Cl
1 2 3
4
5
PPh4Cl, 
CH2Cl2
PPh4
6
Sn Sn
Ph
Cl
Cl
Ph
Cl Cl Cl
+ SnSn Sn
Ph
Cl
Cl
Cl
Cl
Ph
Cl
ClCl
Cl
2PPh4
7
4 PPh4Cl, 
CH2Cl2
8
Sn Sn
Ph
Cl
Cl
Ph
Cl Cl Cl
2PPh4
Cl
C5H6NCl, 
CH2Cl2
9
Sn Sn
Ph
Cl
Cl
Ph
Cl
Cl Cl
2C5H6N
Cl
4 AgCl,
CH2Cl2 − 4 AgI
In the fourth chapter, new ladder-type containing diorganotin oxo-clusters 26– 32, and first
examples of organotin chalcogenides S, Se-adamantane-type structures, 33– 35, containing
both organosilicon and organotin moieties and their exchange reactions are reported. These
chalcogeno organotin clusters are resulted from reactions of the halogenated precursors
MeSi(CH2SnR(3 –n) Xn)3 (n = 0– 3; X = I, Cl, Br; R = Ph, CH2SiMe3) with t-Bu2SnO,
NaOH, EtOH, Na2S and Na2Se (Chart 6. a, b; Chart 7).
205
7. Summary
Chart 6 a). Organotin oxo clusters 26– 27.
Si
Me
Sn
Sn
Sn
Cl
Cl
Me3SiH2C
Me3SiH2C
Cl
Cl
CH2SiMe3
Cl
Cl
12
Si
Me
Sn
Sn
Sn
Cl
Cl
Si
Si
Si
O
O
Cl
Sn
Cl
 (t-Bu2SnO)3
CHCl3
(t-Bu2SnOHCl)2
27
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
Si
Me
Sn
Sn
Sn
O O
Ph
O
SnO t-Bu
t-BuCl
O
Sn
t-Bu Cl
t-Bu
O
Ph
Ph
Sn Sn
Sn
O
O
Ph
Ph
Ph
Si
Me
2
2 (t-Bu2SnO)32 H2O
CHCl3
 4 (t-Bu2SnCl2)  2 HCl
4 26
H
H
 Further Unknown species
+
 Further Unknown species
+
206
7. Summary
Chart 6 b). Organotin oxo clusters 26– 27.
11
(t-Bu2SnO)3
CHCl3
2(t-Bu2SnI2)
28
Si
Me
Sn
Sn
Sn
I
I
Me3SiH2C
Me3SiH2C
I
I
CH2SiMe3
I
I
[MeSi(CH2SnCH2SiMe3O)3]10Si
Me
Sn
Sn
Sn
I
I
Me3SiH2C
Me3SiH2C
I
I
CH2SiMe3
I
I
6 NaOH
CH2Cl2/ MeOHH2O
  6 NaI
Si
Me
Sn
Sn
Sn
I
I
Ph
Ph
I
I
Ph
I
I
(t-Bu2SnO)3,CH2Cl2
  (t-Bu2SnI2)
[MeSi(CH2SnPhO)3]6
Si
Me
Sn
Sn
Sn
Si
Si
Si
O
O
I
Sn
I
O
O
H
H
11
30
3
29
Si
Me
Sn
Sn
Sn
Br
Br
Br
Br
Br
Br
Br
Br
Br
excess EtOH/  H2O
CH2Cl2
Si
Me
Sn
Sn
Si
Me
Sn
Sn
SnSn
O O
O
O
O
Br
O BrO
Br
Br
H
BrO
O
O H
Br
H
H
OHEt
OHEt
9
32
207
7. Summary
Chart 7. Sila-stanna-adamantane 33– 35.
Si
Sn
Sn
Sn
CH2SiMe3
Me3SiH2C S
S
S
Me
Me3SiH2C
Si
Me
Sn
Sn
Sn
I
I
Me3SiH2C
Me3SiH2C
I
I
CH2SiMe3
I
I
3 Na2S, 
acetone/ MeOH/ H2O
− 6 NaI
11 35
Si
Sn
Sn
Sn
Ph
Ph S
S
S
Me
Ph
Si
Me
Sn
Sn
Sn
I
I
Ph
Ph
I
I
Ph
I
I
3 Na2S, 
acetone/ MeOH/ H2O
− 6 NaI
3 33
Si
Sn
Sn
Sn
Ph
Ph Se
Se
Se
Me
Ph
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
3 Na2Se,
αχετονε/ MeOH/ H2O
− 6 NaCl
4 34
In the fifth chapter, reaction of MeClSi((CH2)3SnMeCl2)2, 1, with pyridine gives the new
double- ladder {[MeSi(MeSnCl)(CH2)3(µ3 – O)(MeSnCl)(CH2)3]2O}2, 2 in which, lay-
ers are linked by eight silicon-containing trimethylene chains and four silicon atoms are
forming two siloxanes bridges (Chart 8).
208
7. Summary
Chart 8. Double-ladder {[MeSi(MeSnCl)(CH2)3(µ3-O)(MeSnCl)(CH2)3]2O}2, 2.
Si
Cl
Me
Sn
SnMe
Cl
Cl
Me
Cl
Cl Excess Pyridine/ H2O
CH2Cl24 SiMe
O
Sn
Sn
Me
Cl
Cl
Me
ClCl
Si
Me
Sn
Sn
Me
Me
Si
Me
Sn
Sn
Me
Me
SiO
Me
Sn
Sn
Me
Cl
Cl
Me
Cl
Cl
O
O
O
O
1
2
The final chapter reports synthesis and characterization of amino-stannane
Ph3Sn(CH2)2NH2, 1, aminoalkanol organotin Ph3Sn(CH2)2NH2(CH2CMe2OH)2,
2 and spiro-type compound [Ph3Sn(CH2)2NH2(CH2CMe2O)2]2Sn, 3 as potential
precursors to synthesize future tin functionalized azido-cryptands (Chart 9).
Chart 9. Aminoalkanol organostannane compounds 1– 3.
209
8. Zusammenfassung
Das Hauptziel dieser Arbeit waren die Synthese und Charakterisierung von tripodalen
Tris-(organostannylmethyl) silanen vom Type MeSi(CH2SnR(3 –n)Xn)3 (n = 0– 3; X = I, F,
Cl, Br; R = Ph, CH2SiMe3) als Bausteine für die Synthese neuartiger Organostannatkom-
plexe und beispielloser Organozinn-Chlacogeno-Clustern, darunter neuartige dreieckige
gürtelförmige Diorganotin-Oxo-Clustern [MeSi(CH2SnRO)3]n, R = Ph, CH2SiMe3 mit
gigantischer Nuklearität; Okt okaideka (n = 18) und Trikonta (n = 30). Weiterhin Bildung
neuer spacer-verbrückter Tetrastannane R'Sn(CH2SnR(3 –n)Xn)3, (n = 0– 2; X = I, Cl; R =
Ph, R'= R, X) und deren Versuche zur Komplexierung werden berichtet. Darüber hinaus
wird ein ungewöhnlicher Silizium-Trimethylen-verbrückter Doppelleiter-Organozinn-Oxo-
Cluster synthetisiert. Schließlich werden neue Aminoalkanoltriorganostannan-Derivate als
Vorläufer für den Aufbau zukünftiger zinnfunktionalisierter Azidocryptanden beschrieben.
Die Nummerierung der Verbindungen ist nur in den Kapiteln 2 und 4 verwandt, und in den
Kapiteln 3 und 5- 6 unabhängig. Das DVD enthält Supporting Information von Kapiteln
2- 6.
In Kapitel 2 wurde über eine Reihe neuer Silizium-verbrückter Organozinnverbindungen
MeSi(CH2SnR(3 –n)Xn)3 (n = 0– 3; X = I, F, Cl, Br; R = Ph, CH2SiMe3), 2-12, ihre Syn-
these und Charakterisierung, zusätzlich zur Untersuchung des Komplexierungsverhaltens
der Verbindungen 4– 7, 9 und 12 mit neutraler und geladener Lewis-Base; Cl– , CH3COO– ,
F– , Br– und HMPA berichtet (Abbildung 1, 2. a, b).
210
8. Zusammenfassung
Abbildung 1. Organozinnverbindungen MeSi(CH2SnR(3 –n)Xn)3, 1– 12.
Si
Me
Sn
Sn
Sn
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Si
Me
Sn
Sn
Sn
I
Ph
Ph
Ph
Ph
I
Ph
Ph
I
3 I2,
CH2Cl2
−3 PhI
Si
Me
Sn
Sn
Sn
I
I
Ph
Ph
I
I
Ph
I
I
− 6 PhI
Si
Me
Sn
Sn
Sn
Br
Br
Br
Br
Br
Br
Br
Br
Br
9 Br2,
CH2Cl2
−9 PhBr
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
Si
Me
Sn
Sn
Sn
F
Ph
Ph
Ph
Ph
F
Ph
Ph
F
3 KF,
CH2Cl2/H2O
−3KI
6 AgCl,
CH2Cl2
−6 AgI
6 I2,
CH2Cl2
Si
Me
Sn
Sn
Sn
Br
Br
Ph
Br
Br
Ph
Ph
Br
Br
6 Br2,
CH2Cl2
−6 PhBr
Si
Me
Sn
Sn
Sn
Cl
Ph
Ph
Ph
Ph
Cl
Ph
Ph
Cl
3 AgCl,
CH2Cl2
−3 AgI
3 Me3SiCH2Cl
THF, 55−70°Χ
3 MgClI
C2H4Br2
+Si
Me
Sn
Sn
Sn
CH2SiMe3
Ph
Ph
CH2SiMe3
Ph
Ph
CH2SiMe3
Ph
Ph
3 Mg
Si
Me
Sn
Sn
Sn
CH2SiMe3
I
I
CH2SiMe3 I
I
CH2SiMe3
I
I
6 I2,
CH2Cl2, 0°C
−6 PhI
Si
Me
Sn
Sn
Sn
CH2SiMe3
Cl
Cl
CH2SiMe3
Cl
Cl
CH2SiMe3
Cl
Cl
6 AgCl,
CH2Cl2
−6 AgI
MeSi(CH2Cl)3 + 3 NaSnPh3
THF, −70°Χ −3 NaCl
1
2
3 4
5
6 7
8
9
1011
12
211
8. Zusammenfassung
Abbildung 2 a). Die Organostannatskomplexe 13– 19.
Si
Me
Sn
Sn
Sn
O
O
Ph
Ph
Ph
Ph
O
O
O
Ph
O
Ph
Si Me
Sn
Sn
Sn
O
O
Ph
Ph
Ph
Ph
O
O
O
Ph
O
Ph
Si
Me
Sn
Sn
Sn
I
Ph
Ph
Ph
Ph
I
Ph
Ph
I
6 AgCH3COO,
CH2Cl2
−6 AgI
2
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
4
5
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph Cl
Cl
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
2 C11H21N2Cl, 
CH2Cl2
3 C11H21N2Cl, 
CH2Cl2
C11H21N2 2
C11H21N2 3
Cl
Cl
Cl
Cl Cl
P
O
N
NN
P
O
N
N
N
P
O
NN
N
6 HMPA, 
CH2Cl2
13
14
16
17
Si
Me
Sn
Sn
Sn
Cl
Ph
Ph
Ph
Ph
Cl
Ph
Ph
Cl
6
Si
Me
Sn
Sn
SnPh
Cl
Ph
Ph
Ph
Ph
Ph
P
O
N
N
N
18
P
O
N
N
N
Cl
Cl
Si
Me
Sn
Sn
Sn
Cl
Ph
Ph
Ph
Cl
Ph
Ph
Ph
Cl
P
O
N
NN
P
O
N
N
N
P
O
NN
N
19
· HMPA
+
4 HMPA, 
CH2Cl2
3 HMPA, 
CH2Cl2
Si
Me
Sn
Sn
Sn
Ph
Cl
Cl
Ph
Cl
Cl
Ph
Cl
Cl
NO3
 NO3PPh4, 
CH2Cl2
15
Si
Me
Sn
Sn
Sn
Ph
Cl Ph
Ph
Ph
Ph
Ph
P
O
N
N
N
P
O
N
N
N
Cl
Cl
+
(1)
(2)
PPh4
Abbildung 2 b). Die Organostannatskomplexe 20– 25.
In Kapitel 3, wurde über die Synthese und Charakterisierung von R'Sn(CH2SnR(3 –n)Xn)3,
(n = 0– 2; X = I, Cl; R = Ph, R'= R, X) Derivaten berichtet. Komplexierungsversuche des
Derivats ClSn(CH2SnPhCl2)3, 3 mit Cl– Anionen ergaben interessante zweikernige und
dreikernige Organostannate 6– 9 (Abbildung 3).
212
8. Zusammenfassung
Abbildung 3. R'Sn(CH2SnR(3 –n)Xn)3 Derivate 2– 5 und Organostannatskomplexe 6– 9.
Sn
I
Sn
Sn
Sn
I
Ph
Ph
Ph
Ph
I
Ph
Ph
I
   4 I2,
CH2Cl2
− 4 PhI
Sn
Cl
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
7.5 HCl,
Diethyl ether
− 7 PhCl
Ph
Sn
Ph
Ph
Br Sn
Ph
Cl
Cl
Cl
+3 Sn
Ph
Sn
Sn
Sn
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
− 3 MgClBr
3.5 Mg,
THF, 75°C
Sn
Cl
Sn
Sn
Sn
Cl
Ph
Ph
Ph
Ph
Cl
Ph
Ph
Cl
1 2 3
4
5
PPh4Cl, 
CH2Cl2
PPh4
6
Sn Sn
Ph
Cl
Cl
Ph
Cl Cl Cl
+ SnSn Sn
Ph
Cl
Cl
Cl
Cl
Ph
Cl
ClCl
Cl
2PPh4
7
4 PPh4Cl, 
CH2Cl2
8
Sn Sn
Ph
Cl
Cl
Ph
Cl Cl Cl
2PPh4
Cl
C5H6NCl, 
CH2Cl2
9
Sn Sn
Ph
Cl
Cl
Ph
Cl
Cl Cl
2C5H6N
Cl
4 AgCl,
CH2Cl2 − 4 AgI
In Kapitel 4, wurden neue Leitertypen Diorganotin-Oxo-Clustern 26– 32 berichtet. Die er-
ste Beispiele von neuen Organozinn-Chalkogenide Adamantansverbindungen 33– 35, die
sowohl Organosilizium- als auch Organozinn-Einheiten enthalten, und ihre Austauschreak-
tionen wurden beschrieben. Diese Chalkogen-Organozinn-Cluster resultieren aus Reak-
tionen der halogenierten Vorläufer MeSi(CH2SnR(3 –n)Xn)3 (n = 0– 3; X = I, F, Cl, Br;
R = Ph, CH2SiMe3) mit t-Bu2SnO, NaOH, EtOH, Na2S und Na2Se (Abbildung 4. a, b;
Abbildung 5).
Abbildung 4 a). Organozinn-Oxo-Clustern 26– 27.
Si
Me
Sn
Sn
Sn
Cl
Cl
Me3SiH2C
Me3SiH2C
Cl
Cl
CH2SiMe3
Cl
Cl
12
Si
Me
Sn
Sn
Sn
Cl
Cl
Si
Si
Si
O
O
Cl
Sn
Cl
 (t-Bu2SnO)3
CHCl3
(t-Bu2SnOHCl)2
27
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
Si
Me
Sn
Sn
Sn
O O
Ph
O
SnO t-Bu
t-BuCl
O
Sn
t-Bu Cl
t-Bu
O
Ph
Ph
Sn Sn
Sn
O
O
Ph
Ph
Ph
Si
Me
2
2 (t-Bu2SnO)32 H2O
CHCl3
 4 (t-Bu2SnCl2)  2 HCl
4 26
H
H
 Further Unknown species
+
 Further Unknown species
+
213
8. Zusammenfassung
Abbildung 4 b). Organozinn-Oxo-Clustern 28– 32.
11
(t-Bu2SnO)3
CHCl3
2(t-Bu2SnI2)
28
Si
Me
Sn
Sn
Sn
I
I
Me3SiH2C
Me3SiH2C
I
I
CH2SiMe3
I
I
[MeSi(CH2SnCH2SiMe3O)3]10Si
Me
Sn
Sn
Sn
I
I
Me3SiH2C
Me3SiH2C
I
I
CH2SiMe3
I
I
6 NaOH
CH2Cl2/ MeOHH2O
  6 NaI
Si
Me
Sn
Sn
Sn
I
I
Ph
Ph
I
I
Ph
I
I
(t-Bu2SnO)3,CH2Cl2
  (t-Bu2SnI2)
[MeSi(CH2SnPhO)3]6
Si
Me
Sn
Sn
Sn
Si
Si
Si
O
O
I
Sn
I
O
O
H
H
11
30
3
29
Si
Me
Sn
Sn
Sn
Br
Br
Br
Br
Br
Br
Br
Br
Br
excess EtOH/  H2O
CH2Cl2
Si
Me
Sn
Sn
Si
Me
Sn
Sn
SnSn
O O
O
O
O
Br
O BrO
Br
Br
H
BrO
O
O H
Br
H
H
OHEt
OHEt
9
32
214
8. Zusammenfassung
Abbildung 5. Silastannaadamantane 33– 35.
Si
Sn
Sn
Sn
CH2SiMe3
Me3SiH2C S
S
S
Me
Me3SiH2C
Si
Me
Sn
Sn
Sn
I
I
Me3SiH2C
Me3SiH2C
I
I
CH2SiMe3
I
I
3 Na2S, 
acetone/ MeOH/ H2O
− 6 NaI
11 35
Si
Sn
Sn
Sn
Ph
Ph S
S
S
Me
Ph
Si
Me
Sn
Sn
Sn
I
I
Ph
Ph
I
I
Ph
I
I
3 Na2S, 
acetone/ MeOH/ H2O
− 6 NaI
3 33
Si
Sn
Sn
Sn
Ph
Ph Se
Se
Se
Me
Ph
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
3 Na2Se,
αχετονε/ MeOH/ H2O
− 6 NaCl
4 34
In Kapitel 5, die Reaktion vonMeClSi((CH2)3SnMeCl2)2, 1 mit Pyridin gab die neue
Doppelleiter {[MeSi(MeSnCl)(CH2)3(µ3 – O)(MeSnCl)(CH2)3]2O}2, 2, in der die zwei
Leitern durch acht siliziumhaltige Trimethylenketten verbunden sind. Vier Silizium Atome
bilden zwei Siloxanbrücken (Abbildung 6).
215
8. Zusammenfassung
Abbildung 6. Doppelleiter {[MeSi(MeSnCl)(CH2)3(µ3 – O)(MeSnCl)(CH2)3]2O}2, 2.
Si
Cl
Me
Sn
SnMe
Cl
Cl
Me
Cl
Cl Excess Pyridine/ H2O
CH2Cl24 SiMe
O
Sn
Sn
Me
Cl
Cl
Me
ClCl
Si
Me
Sn
Sn
Me
Me
Si
Me
Sn
Sn
Me
Me
SiO
Me
Sn
Sn
Me
Cl
Cl
Me
Cl
Cl
O
O
O
O
1
2
Das letzte Kapitel berichtete über die Synthese und Charakterisierung von Aminostannane
Ph3Sn(CH2)2NH2, 1, Aminoalkanolorganostannane Ph3Sn(CH2)2NH2(CH2CMe2OH)2,
2 und Spiro-Verbindung [Ph3Sn(CH2)2NH2(CH2CMe2O)2]2Sn, 3 als potenzielle Vor-
läufer für die Synthese zukünftiger zinnfunktionalisierter Azido-Kryptanden (Abbildung
7).
216
8. Zusammenfassung
Abbildung 7. Aminoalkanolorganostannane-Verbindungen 1– 3.
217
9. References
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221
List of New Compounds
List of New Compounds
Chapter 2
Si
Me
Sn
Sn
Sn
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Si
Me
Sn
Sn
Sn
I
Ph
Ph
Ph
Ph
I
Ph
Ph
I
Si
Me
Sn
Sn
Sn
I
I
Ph
Ph
I
I
Ph
I
I
Si
Me
Sn
Sn
Sn
Br
Br
Br
Br
Br
Br
Br
Br
Br
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
Si
Me
Sn
Sn
Sn
F
Ph
Ph
Ph
Ph
F
Ph
Ph
F
Si
Me
Sn
Sn
Sn
Br
Br
Ph
Br
Br
Ph
Ph
Br
Br
Si
Me
Sn
Sn
Sn
Cl
Ph
Ph
Ph
Ph
Cl
Ph
Ph
Cl
2 3 4
5 6 7
8 9
11
Si
Me
Sn
Sn
Sn
CH2SiMe3
I
I
CH2SiMe3
I
I
CH2SiMe3
I
I
10
Si
Me
Sn
Sn
Sn
CH2SiMe3
Ph
Ph
CH2SiMe3
Ph
Ph
CH2SiMe3
Ph
Ph
12
Si
Me
Sn
Sn
Sn
CH2SiMe3
Cl
Cl
CH2SiMe3
Cl
Cl
CH2SiMe3
Cl
Cl
222
List of New Compounds
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph Cl
Cl
Si
Me
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
C11H21N2 2
C11H21N2 3
Cl
Cl
Cl
Cl Cl
P
O
N
N
N
P
O
N
N
N
P
O
NN
N
13
14
16
Si
Me
Sn
Sn
Sn
Ph
Cl
Cl
Ph
Cl
Cl
Ph
Cl
Cl
NO3
15
PPh4
223
List of New Compounds
Si
Me
Sn
Sn
Sn
O
O
Ph
Ph
Ph
Ph
O
O
O
Ph
O
Ph
Si Me
Sn
Sn
Sn
O
O
Ph
Ph
Ph
Ph
O
O
O
Ph
O
Ph
17
Si
Me
Sn
Sn
SnPh
Cl
Ph
Ph
Ph
Ph
Ph
P
O
N
N
N
18
P
O
N
N
N
Cl
Cl
Si
Me
Sn
Sn
Sn
Cl
Ph
Ph
Ph
Cl
Ph
Ph
Ph
Cl
P
O
N
N
N
P
O
N
N
N
P
O
NN
N
19
· HMPA
+ Si
Me
Sn
Sn
Sn
Ph
Cl Ph
Ph
Ph
Ph
Ph
P
O
N
N
N
P
O
N
N
N
Cl
Cl
+
224
List of New Compounds
Si
Me
Sn
Sn
Sn
Si
Me
Sn
Sn
Sn
F
F
F
F
Ph
F
Ph
Ph
Ph
F
F
PhPh
F
Ph Ph
Ph
Ph
Ph
Ph
NEt4 2
22
PPh4 Si
Me
Sn
Sn
Sn
Br
Br
Br
Br
Br
Br
Br Br
Br
Br Si
Me
Sn
Sn
Sn
Br
Br
Br
Br
Br
Br
Br Br
Br
Br
Br
NEt4
2
23 24
Si
Me
Sn
Sn
Sn
Cl
Cl
CH2SiMe3
CH2SiMe3
Cl Cl
ClCl
C11H21N2 2
CH2SiMe3
Cl
Cl
25
Si
Me
Sn
Sn
Sn
Cl
Ph
Ph
Ph
Ph
Cl
Ph Cl
Ph
PPh4 Cl
20
Si
Me
Sn
Sn
Sn
Cl
Ph
Ph
Ph
Ph
Cl
Ph
Cl
2
Ph
Cl
Cl
21
PPh4
225
List of New Compounds
Chapter 3
Sn
I
Sn
Sn
Sn
I
Ph
Ph
Ph
Ph
I
Ph
Ph
I
Sn
Cl
Sn
Sn
Sn
Cl
Cl
Ph
Ph
Cl
Cl
Ph
Cl
Cl
Sn
Ph
Sn
Sn
Sn
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Sn
Cl
Sn
Sn
Sn
Cl
Ph
Ph
Ph
Ph
Cl
Ph
Ph
Cl
2 3
4 5
PPh4
6
Sn Sn
Ph
Cl
Cl
Ph
Cl Cl Cl
SnSn Sn
Ph
Cl
Cl
Cl
Cl
Ph
Cl
ClCl
Cl
2PPh4
7
8
Sn Sn
Ph
Cl
Cl
Ph
Cl Cl Cl
2PPh4
Cl
9
Sn Sn
Ph
Cl
Cl
Ph
Cl
Cl Cl
2C5H6N
Cl
226
List of New Compounds
Chapter 4
[MeSi(CH2SnPhO)3]6
Si
Me
Sn
Sn
Sn
Cl
Cl
Si
Si
Si
O
O
Cl
Sn
Cl
27
28
Si
Me
Sn
Sn
Sn
Si
Si
Si
O
O
I Sn
I
O
O
H
H
Si
Me
Sn
Sn
Sn
O O
Ph
O
SnO t-Bu
t-BuCl
O
Sn
t-Bu Cl
t-Bu
O
Ph
Ph
Sn Sn
Sn
O
O
Ph
Ph
Ph
Si
Me 26
H
H
29
[MeSi(CH2SnCH2SiMe3O)3]10
30
Si Me
Sn
Sn
SiMe
Sn
Sn
SnSn
O O
O
O
O
Br
O BrO
Br
Br
H
BrO
O
O H
Br
H
H
OHEt
OHEt
32
Si
Me
Sn
Sn
Sn
O O
Ph
O
SnO t-Bu
t-BuI
O
Sn
t-Bu I
t-Bu
O
Ph
Ph
Sn Sn
Sn
O
O
Ph
Ph
Ph
Si
Me 31
H
H
227
List of New Compounds
Si
Sn
Sn
Sn
Ph
Ph S
S
S
Me
Ph
33
Si
Sn
Sn
Sn
Ph
Ph Se
Se
Se
Me
Ph
34
Si
Sn
Sn
Sn
CH2SiMe3
Me3SiH2C S
S
S
Me
Me3SiH2C
35
Chapter 5
Si
Me
O
Sn
Sn
Me
Cl
Cl
Me
ClCl
Si
Me
Sn
Sn
Me
Me
Si
Me
Sn
Sn
Me
Me
SiO
Me
Sn
Sn
Me
Cl
Cl
Me
Cl
Cl
O
O
O
O
2
228
List of New Compounds
Chapter 6
Sn
Ph
Ph Ph
NH2
Sn
Ph
Ph Ph
N OH
OH
1 2
Sn
Ph
PhPh
NO
O
Sn
O
O
Sn
Ph
Ph
Ph
N
3
229
Appendix
Appendix
Experimental Procedures
All solvents were dried and purified according to standard procedures and freshly distilled
prior to use. MeSi(CH2Cl)3,[24] NaSnPh3,[12] and (t-Bu2SnO)3[22] were synthesized ac-
cording to the literature. Ph3SnCl, MeSiCl3, elemental iodine, and silver chloride were
commercially available. They were used without further purification. The 1H, 13C, 29Si
and 119Sn NMR spectra were recorded on Bruker DPX-400, DRX-600, and AVIII-600
spectrometers. Solution 1H, 13C, 29Si and 119Sn NMR chemical shifts δ are given in ppm
and were referenced to Me4Si (1H, 13C, 29Si), and Me4Sn (119Sn). Elemental analyses
were performed on a LECO-CHNS-932 analyzer. The electrospray mass spectra were
recorded with a Thermoquest-Finnigan instrument. The samples were introduced as solu-
tion in CH3CN or CH2Cl2 through a syringe pump operating at 0.5 µL min−1. The capillary
voltage was 4.5 kV, whereas the cone skimmer voltage was varied between 50 and 250 kV.
Identification of the expected ions was assisted by comparison of experimental and calcu-
lated isotope distribution patterns. The m/z values reported correspond to those of the most
intense peak in the corresponding isotope pattern. Melting points were determined using
a Büchi Melting Point M-560. IR spectra (ATR) were recorded on a PerkinElmer FTIR
spectrometer.The DOSY (diffusion-ordered spectroscopy) measurement was performed
with a pulse sequence using double stimulated echo for convection compensation and
LED and bipolar gradient pulses for diffusion.[67] The measurements were executed with
an AVANCE-III HD 600 MHz NMR spectrometer equipped with a 5 mm heliumcooled
BBFO probe from Bruker BioSpin GmbH (Rheinstetten,Germany). Thirty-two different
gradient strengths varying between 3% and 95% of the maximum strength of 53 G/cm
were used. Thirty-two scans per gradient strength were acquired with 16 kB data points
of the FID (acquisition time of 0.97 s) and a relaxation delay of 1.5 s. According to the
DOSY figure, the expansion indicates one conformational rearrangement of the compound
in solution with diffusion coefficient of 3.89×10−10(± 1×10−11) m2 s−1. Single crystal
X-ray diffraction data was collected with either an Oxford Diffraction Xcalibur, equipped
with a Saphire3 CCD detector and an Enhance fine focus sealed tube (Mo-Kα), or a Stoe
StadiVari, equipped with a Pilatus 200K HPC detector and a GeniX 3D microfocus sealed
tube (Cu-Kα , Xenocs), by using ω-scans. Data collection, integration, absorption correc-
tion and space group determination were performed with the respective software packages
CrysAlisPro (2014 and 2019) or X-Area (2018). Structure solutions were obtained with
ShelXS (2008 and 2013) using the direct method. The structure models were refined by
230
Appendix
using ShelXL (2018) with a least squares procedure against F2. Unresolved electron den-
sity was subtracted from the structure factor by applying a solvent mask in the software
package OLEX2.
Crystallographic data
Chapter 2
2 6 9
CCDC number 1995881
Chemical formula C58H54SiSn3 C40H39Cl3SiSn3 C4H9Br9SiSn3
Mr (g · mol−1) 1135.17 1010.22
Crystal system Monoclinic Orthorhombic Orthorhombic
Space group P21/c Pna21 Pna21
Temperature (K) 173 105 173(2)
a, b, c (Å) 18.2220(5), 10.8715(3),
26.1335(7)
23.0159(8), 23.161(5),
16.1580(5)
13.014(2), 12.1225(8),
14.2155(9)
α , β , γ (◦) 90, 98.067(3), 90 90, 90, 90 90, 90, 90
V (Å3) 5125.8 (2) 3998.7(2) 2242.7(4)
Z 4 4 4
Radiation type Mo Kα Mo Kα (λ = 0.71073) –
µ (mm−1) 1.51 2.117 19.386
Crystal size (mm3) 0.21 × 0.19 × 0.19 0.2 × 0.15 × 0.01 0.250 x 0.050 x 0.040
Rint 0.037 2 0.0435
θmax (◦)Range 30.6 4.182 to 59.594 2.208 to 25.491
(sin θ /λ )max (Å−1) 0.725 0.556
R[F2 > 2s(F2)],
wR(F2),S
0.032, 0.073, 1.030 R1 = 0.0290, wR2 =
0.0700
R1 = 0.0374, wR2 =
0.0708
No. of reflections 54829 26955 6116
No. of reflections inde-
pendent
14937 3754
No. of reflections ob-
served
11515
No. of parameters 536
No. of restraints 72
ρmax, ρmin (e Å−3) 0.63, -0.51 0.808, -0.985
231
Appendix
13.2C7H8 14 16
Chemical formula C58H82Cl8N4SiSn3·
2C7H8
C55H87Cl9N6SiSn3 C40H78Cl6N9O3P3SiSn3
Mr (g·mol−1) 1503.03 1535.51 1422.89
Crystal system Monoclinic Orthorhombic Trigonal
Space group P21/n Pna21 Rint
Temperature (K) 173(2) 173(2) 110(2)
a, b, c (Å) 11.8366(12),
19.4910(13),
29.6994(19)
26.5310(16), 23.518(3),
11.5221(8)
24.9951(6), 24.9951(6),
16.6505(5)
α , β , γ (◦) 90, 98.085(7), 90 90, 90, 90 90, 90, 120
V (Å3) 6851.9(9 7189.4(11) 15444 (6)
Z 4 4 2
µ (mm−1) 1.451 1.421 20.73
Crystal size (mm3) 0.119 x 0.087 x 0.046 0.200 x 0.075 x 0.042 0.48 x 0.35 x 0.25
Rint 0.1655 0.1125 0.0354
θmax (◦) Range 2.126 to 27.500 2.314 to 25.499 5.548 to 61.428
R[F2 > 2s(F2)],
wR(F2),S
R1 = 0.0650, wR2 =
0.1006
R1 = 0.0698, wR2 =
0.1584
R1 = 0.0205, wR2 =
0.0478
No. of reflections 58734 37793 49081
No. of reflections inde-
pendent
15750 12994 5883
ρmax, ρmin (e Å−3) 0.712, -0.776 2.448, -0.932 0.67, -0.41
232
Appendix
17 18 19
Chemical formula C92H96O12Si2Sn6 C52H75Cl3N6O2P2SiSn3 C64H111Cl3N12O4P4SiSn3
Mr (g · mol−1) 2162 1368.63 1727.03
Crystal system Triclinic Triclinic Monoclinic
Space group P-1 P-1 P21/n
Temperature (K) 173(2) 100(1) 99.98(17)
a, b, c (Å) 12.2110(18), 14.678(2),
14.917(2)
10.2180(7),
22.1006(15), 28.628(2)
15.2069(6), 18.7712(7),
15.4720(7)
α , β , γ (◦) 64.521(13), 85.400(11),
69.401(13)
79.834(2), 87.530(2),
76.903(2)
90, 116.993(5), 90
V (Å3) 2251.3(6) 6197.8(7) 3935.4(3)
Z 2 4 2
µ (mm−1) 1.723 1.441 1.194
Crystal size (mm3) 0.306 x 0.169 x 0.029 0.15 x 0.135 x 0.06 0.79 x 0.47 x 0.24
Rint 0.0752 0.1628 0.0445
θmax (◦) Range 2.441 to 25.500 3.866 to 55 5.082 to 60.976
R[F2 > 2s(F2)],
wR(F2),S
R1 = 0.1293, wR2 =
0.3790
R1 = 0.0737, wR2 =
0.1526
R1 = 0.0431, wR2 =
0.1039
No. of reflections 19675 198935 49902
No. of reflections inde-
pendent
8382 28460 20736
ρmax, ρmin (e Å−3) 3.77, -1.804 1.69, -1.25 1.62, -0.78
22 23.0.5CH2Cl2
Chemical formula C96H118F8N2Si2Sn6 C20H49Br11N2SiSn3
Mr (g · mol−1) 2220.24 1622.2
Crystal system Monoclinic Triclinic
Space group P21/n P-1
Temperature (K) 173(2) 173(2)
a, b, c (Å) 16.6900(8), 10.9201(5),
26.0626(11)
7.1210(2), 17.0419(6),
18.8069(6)
α , β , γ (◦) 90, 91.970(4), 90 103.058(3), 99.286(3), 91.524(3)
V (Å3) 4747.3(4) 2189.44(12)
Z 4 2
µ (mm−1) 1.639 10.969
Crystal size (mm3) 0.190 x 0.051 x 0.040 0.349 x 0.106 x 0.035
Rint 0.0513 0.0463
θmax (◦) Range 2.229 to 30.500 2.257 to 25.499
R[F2 > 2s(F2)], wR(F2),S R1 = 0.0707, wR2 = 0.1934 R1 = 0.0360, wR2 = 0.0915
No. of reflections 45664 26948
No. of reflections independent 14488 8169
ρmax, ρmin (e Å−3) 3.295, -1.185 1.118 and -1.052
233
Appendix
25.0.5CH2Cl2 24
Chemical formula C38.50H85Cl9N4Si4Sn3 C28.5H30Br10ClPSiSn3
Mr (g · mol−1) 1391.58 1422.89
Crystal system Triclinic Orthorhombic
Space group P-1 Pba2
Temperature (K) 173(2) 173(2)
a, b, c (Å) 11.8657(4), 14.9245(5),
20.4810(6)
13.8538(4), 44.2038(15),
7.0299(2)
α , β , γ (◦) 84.913(3), 88.409(3), 82.289(3) 90, 90, 90
V (Å3) 3579.6(2) 4305.0(2)
Z 2 4
µ (mm−1) 1.466 11.980
Crystal size (mm3) 0.299 x 0.170 x 0.022 0.500 x 0.149 x 0.126
Rint 0.0580 0.0559
θmax (◦) Range 2.232 to 29.000 2.357 to 25.498
R[F2 > 2s(F2)], wR(F2),S R1 = 0.0520, wR2 = 0.1572 R1 = 0.0670, wR2 = 0.1606
No. of reflections 69525 31806
No. of reflections independent 19013 8010
ρmax, ρmin (e Å−3) 2.512, -0.770 2.570 and -1.526
Chapter 3
2 4 6
Chemical formula C63H56Sn4 C39H36I4Sn4 C37H32Cl5PSn2
Mr (g · mol−1) 1287.83 1487.04 922.22
Crystal system Triclinic Triclinic Triclinic
Space group P-1 P-1 P-1
Temperature (K) 173(2) 173(2) 173(2)
a, b, c (Å) 9.8140(5), 15.1499(9),
19.0164(9)
10.1840(3), 13.3604(4),
17.8331(5)
11.5330(5), 11.7687(7),
14.5287(10)
α , β , γ (◦) 102.424(5), 98.750(4),
98.610(5)
69.866(2), 76.357(2),
82.041(2)
68.339(6), 87.365(5),
80.461(4)
V (Å3) 2679.8(3) 2209.49(12) 1807.1(2)
Z 2 2 2
µ (mm−1) 1.881 5.054 1.822
Crystal size (mm3) 0.18 x 0.10 x 0.05 0.30 x 0.19 x 0.12 0.210 x 0.170 x 0.140
Rint 0.0483 0.0333 0.0244
θmax (◦) Range 2.138 to 25.500 2.181 to 25.499 2.322 to 25.500
R[F2 > 2s(F2)],
wR(F2),S
R1 = 0.0432, wR2 =
0.0975
R1 = 0.0260, wR2 =
0.0571
R1 = 0.0395, wR2 =
0.1159
No. of reflections 26160 42994 13587
No. of reflections inde-
pendent
9972 8222 6724
ρmax, ρmin (e Å−3) 0.773, -0.844 1.248, -1.240 2.999, -1.124
234
Appendix
7 8.0.5H2O 9
Chemical formula C62H54Cl8P2Sn3 C122H111O0.5Cl12P4Sn4 C23H24Cl6N2Sn2
Mr (g · mol−1) 1500.66 2600.36 778.52
Crystal system Triclinic Monoclinic Monoclinic
Space group P-1 P21/n P21/c
Temperature (K) 173(2) 173(2) 173(2)
a, b, c (Å) 9.9526(4), 12.5607(5),
13.4456(6)
17.6121(5), 15.0792(4),
44.4098(16)
12.9246(13),
15.7566(9),
15.1585(13)
α , β , γ (◦) 69.583(4), 75.496(4),
75.580(4)
90, 92.667(3), 90 90, 115.060(10), 90
V (Å3) 1500.66(12) 11781.4(6) 2796.4(5)
Z 1 2 4
µ (mm−1) 1.687 1.282 2.375
Crystal size (mm3) 0.100 x 0.080 x 0.070 0.380 x 0.310 x 0.250 0.280 x 0.120 x 0.110
Rint 0.0296 0.0543 0.0315
θmax (◦) Range 2.454 to 25.499 2.216 to 25.500 2.731 to 25.499
R[F2 > 2s(F2)],
wR(F2),S
R1 = 0.0391, wR2 =
0.1249
R1 = 0.0482, wR2 =
0.0938
R1 = 0.0293, wR2 =
0.0639
No. of reflections 17230 68966 5856
No. of reflections inde-
pendent
5584 21918 3640
ρmax, ρmin (e Å−3) 1.268, -1.094 0.600, -1.535 0.401, -0.468
235
Appendix
Chapter 4
26 27 28
Chemical formula C60H88Cl2O8Si2Sn8 C24H60Cl4O2Si4Sn4 C24H62I2O4Si4Sn4
Mr (g · mol−1) 1005.94 1109.64 1255.65
Crystal system Monoclinic Monoclinic monoclinic
Space group C2/c P21/c P21/c
Temperature (K) 173(2) 173(2) 105(1)
a, b, c (Å) 26.5865(15),
22.6357(13),
15.1998(10)
15.0807(18),
11.8774(12),
23.6920(19)
14.7561(4), 22.9312(8),
12.9476(5)
α , β , γ (◦) 90, 101.705(6), 90 90, 94.086(9), 90 90, 98.205(3), 90
V (Å3) 8957.1(10) 4232.9(7) 4336.3(2)
Z 8 4 4
µ (mm−1) 2.316 2.719 3.836
Crystal size (mm3) 0.265 x 0.038 x 0.026 0.082 x 0.073 x 0.046 0.6 x 0.38 x 0.18
Rint 0.1039 0.1544 0.236
θmax (◦) Range 2.514 to 27.499 2.115 to 28.997 2.777 to 30.0240
R[F2 > 2s(F2)],
wR(F2),S
R1 = 0.0505, wR2 =
0.1049
R1 = 0.0706, wR2 =
0.1325
R1 = 0.0374, wR2 =
0.999
No. of reflections 38491 34347 22164
No. of reflections inde-
pendent
10295 11261 8276
ρmax, ρmin (e Å−3) 0.957, -0.951 1.134, -1.484 Max 0.906
236
Appendix
29 30 31.5DMF
CCDC number 1995233 1953399
Chemical formula C132H144O18Si6Sn18 ·
6CH2Cl2
C160H414O30Si40Sn30 ·
8CH2Cl2
C75H121I2N5O13Si2Sn8
Mr (g · mol−1) 4323.42 7503.19 2560.26
Crystal system Monoclinic Triclinic Monoclinic
Space group P21/n P-1 P21/n
Temperature (K) 173 100 100
a, b, c (Å) 14.0911 (5), 32.306 (2),
37.0724 (12)
16.822 (3), 23.161 (5),
41.207 (8)
22.831(5), 16.825(3),
24.945(5)
α , β , γ (◦) 90, 97.086 (4), 90 88.47 (3), 86.28
(3),74.59 (3)
90, 101.53(3), 90
V (Å3) 16747.4 (13) 15444 (6) 9389(3)
Z 4 2 4
Radiation type Mo Kα Cu Kα –
µ (mm−1) 2.72 20.73 2.830
Crystal size (mm) 0.19 × 0.13 × 0.04 0.14 × 0.08 × 0.02 0.19 × 0.123 × 0.030
Rint 0.077 0.090 0.0690
θmax (◦) 23.3 60.1 25.123
(sinθ/ lambda)max (Å-
1)
0.556 0.562 –
R[F2 > 2s(F2)],
wR(F2),S
0.065, 0.131, 0.920 0.128, 0.350, 0.840 wR2 = 0.1904, S =
0.939
No. of reflections 52875 57472 16758
No. of reflections inde-
pendent
24054 33542 16672
No. of reflections ob-
served
13695 11350 10485
No. of parameters 1511 1183 –
No. of restraints 417 31 –
ρmax, ρmin (e Å−3) 1.03, -0.80 1.26, -1.42 –
237
Appendix
32 33
Chemical formula C20H54Br6O12Si2Sn6 C22H24S3SiSn3
Mr (g · mol−1) 1734.41 765.73
Crystal system Monoclinic Trigonal
Space group P21/n R3c
Temperature (K) 173(2) 100(2)
a, b, c (Å) 9.5284(9), 17.1420(15),
14.7373(15)
12.4403(3), 12.4403(3),
29.1857(16)
α , β , γ (◦) 90, 108.393(11), 90 90, 90, 120
V (Å3) 2284.2(4) 3911.7(3)
Z 2 6
µ (mm−1) 8.575 2.719
Crystal size (mm3) 0.350 x 0.030 x 0.020 0.185 x 0.100 x 0.088
Rint 0.1272 0.0226
θmax (◦) Range 2.264 to 25.499 3.275 to 25.446
R[F2 > 2s(F2)], wR(F2),S R1 = 0.0523, wR2 = 0.1203 R1 = 0.0166, wR2 = 0.0363
No. of reflections 30171 6706
No. of reflections independent 4252 1487
ρmax, ρmin (e Å−3) 1.394, -1.311 0.398, -0.359
35 34
Chemical formula C16H42S3Si4Sn3 C22H24Se3SiSn3
Mr (g · mol−1) 799.10 909.45
Crystal system Monoclinic Monoclinic
Space group P121/c P21/c
Temperature (K) 173.15 173(2)
a, b, c (Å) 12.6438(4), 11.7267(5),
42.4292(17)
12.1798(3), 13.9112(4),
16.1275(5)
α , β , γ (◦) 90, 97.246(3), 90 90, 98.468(2), 90
V (Å3) 6240.7(4) 2702.78(13)
Z 8 4
µ (mm−1) 2.740 6.843
Crystal size (mm3) 0.081 x 0.073 x 0.054 0.301 x 0.242 x 0.213
Rint 0.0804 0.0495
θmax (◦) Range 2.264 to 25.499 2.236 to 28.996
R[F2 > 2s(F2)], wR(F2),S R1 = 0.0706, wR2 = 0.1075 R1 = 0.0231, wR2 = 0.0490
No. of reflections 47531 37776
No. of reflections independent 11615 6661
ρmax, ρmin (e Å−3) 1.944, -1.917 1.050 and -0.673
238
Appendix
Chapter 5
2
Chemical formula C72O12Cl16Si8Sn16
Mr (g · mol−1) 3748.07
Crystal system Monoclinic
Space group P21/n
Temperature (K) 173.15
a, b, c (Å) 8.7441(17), 18.6157(37), 22.0047(44)
α , β , γ (◦) 90, 92.618(30), 90
V (Å3) 3578.13(123)
Z 4
µ (mm−1) –
Crystal site (mm3) –
Rint –
θmax (◦) Range –
R[F2 > 2s(F2),wR(F2),S] –
No. of reflections –
No. of reflections independent –
ρmax, ρmin (e Å−3) –
239
Appendix
Chapter 6
1 2 3.C7H8
Chemical formula C20H21NSn C28H37NO2Sn C56H70N2O4Sn3 ·C7H8,
C3 ·5;
C66.50H78N2O4Sn3
Mr (g · mol−1) 394.07 538.27 1325.37
Crystal system Monoclinic Monoclinic triclinic
Space group P21/n P21/c P-1
Temperature (K) 173(2) 173(2) 105
a, b, c (Å) 9.7902(3), 11.5823(3),
31.0993(9)
23.092(2), 6.4775(5),
19.2207(12)
9.5316(2), 15.9036(4),
21.5036(6)
α , β , γ (◦) 90, 92.621(2), 90 90, 112.224(8), 90 76.996(2), 77.796(2),
75.614(2)
V (Å3) 3522.75(17) 2661.4(4) 3034.43(15)
Z 8 4 2
µ (mm−1) 1.447 0.983 1.451
Crystal size (mm3) 0.213 x 0.199 x 0.058 0.228 x 0.089 x 0.065 0.15 x 0.15 x 0.05
Rint 0.0288 0.0664 0.0332
θmax (◦) Range 2.193 to 29.500 2.289 to 30.500 2.6350 to 29.4410
R[F2 > 2s(F2)],
wR(F2),S
R1 = 0.0344, wR2 =
0.0712
R1 = 0.0730, wR2 =
0.1852
R1 = 0.0335
No. of reflections 20249 24152 20722
No. of reflections inde-
pendent
9799 8111 –
ρmax, ρmin (e Å−3) 1.156, -0.658 1.455, -1.066 Max 0.905
240
Eidesstattliche Versicherung (Affidavit) 
 
 
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