Authors: | Gock, Michael Lutter, Michael Pintus, Anna Schollmeier, Dieter Arca, Massimiliano Lippolis, Vito Jurkschat, Klaus |
Title: | Chelating phosphorus–an O, C, O-coordinating pincer-type ligand coordinating PIII and PV centres |
Language (ISO): | en |
Abstract: | The sequence of reactions of the phosphorus-containing aryllithium compound 5-t-Bu-1,3-[(P(O)(O-i-Pr)2]2C6H2Li (ArLi) with Ph2PCl, KMnO4, elemental sulfur and elemental selenium, respectively, gave the aryldiphenylphosphane chalcogenides 5-t-Bu-1,3-[(P(O)(O-i-Pr)2]2C6H2P(E)Ph2 (1, E=O; 2, E=S; 3, E=Se). Compound 1 partially hydrolysed giving [5-t-Bu-1-{(P(O)(O-i-Pr)2}-3-{(P(O)(OH)2}C6H2]P(O)Ph2 (4). The reaction of ArLi with PhPCl2 provided the benzoxaphosphaphosphole [1(P), 3(P)-P(O)(O-i-Pr)OPPh-6-t-Bu-4-P(O)(O-i-Pr)2]C6H2P (5i) as a mixture of the two diastereomers. The oxidation of 5i with elemental sulfur gave the benzoxaphosphaphosphole sulfide [1(P), 3(P)-P(O)(O-i-Pr)OP(S)Ph-6-t-Bu-4-P(O)(O-i-Pr)2]C6H2 (5) as pair of enantiomers P1(R), P3(S)/P1(S), P3(R) of the diastereomer (RS/SR)-5 (5b). The aryldiphenylphosphane 5-t-Bu-1,3-[(P(O)(O-i-Pr)2]2C6H2PPh2 (6) was obtained from the reaction of the corresponding aryldiphenylphosphane sulfide 2 with either sodium hydride, NaH, or disodium iron tetracarbonyl, Na2Fe(CO)4. The oxidation of the aryldiphenylphosphane 6 with elemental iodine and subsequent hydrolysis yielded the aryldiphenyldioxaphosphorane 9-t-Bu-2,6-(OH)-4,4-Ph2-3,5-O2-2,6-P2-4λ5-P-[5.3.1.0]-undeca-1(10),7(11),8-triene (7). Both of its diastereomers, (RR/SS)-7 (7a) and (RS/SR)-7 (7b), were separated as their chloroform and i-propanol solvates, 7a⋅2CHCl3 and 7b⋅i-PrOH, respectively. DFT calculations accompanied the experimental work. |
Subject Headings: | DFT calculations NMR spectroscopy Phosphorus triorganodioxaphosphorane X-ray diffraction |
Subject Headings (RSWK): | Dichtefunktionalformalismus NMR-Spektroskopie Phosphorane Röntgenstreuung |
URI: | http://hdl.handle.net/2003/42323 http://dx.doi.org/10.17877/DE290R-24160 |
Issue Date: | 2022-07-12 |
Rights link: | https://creativecommons.org/licenses/by-nc/4.0/ |
Appears in Collections: | Lehrstühle für Anorganische Chemie |
Files in This Item:
File | Description | Size | Format | |
---|---|---|---|---|
Chemistry A European J - 2022 - Gock - Chelating Phosphorus An O C O‐Coordinating Pincer‐Type Ligand Coordinating PIII.pdf | DNB | 4.32 MB | Adobe PDF | View/Open |
This item is protected by original copyright |
This item is licensed under a Creative Commons License