Chelating phosphorus–an O, C, O-coordinating pincer-type ligand coordinating PIII and PV centres

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dc.contributor.authorGock, Michael
dc.contributor.authorLutter, Michael
dc.contributor.authorPintus, Anna
dc.contributor.authorSchollmeier, Dieter
dc.contributor.authorArca, Massimiliano
dc.contributor.authorLippolis, Vito
dc.contributor.authorJurkschat, Klaus
dc.date.accessioned2024-02-12T12:29:41Z
dc.date.available2024-02-12T12:29:41Z
dc.date.issued2022-07-12
dc.description.abstractThe 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.en
dc.identifier.urihttp://hdl.handle.net/2003/42323
dc.identifier.urihttp://dx.doi.org/10.17877/DE290R-24160
dc.language.isoende
dc.relation.ispartofseriesChemistry - a European journal;28(58)
dc.rights.urihttps://creativecommons.org/licenses/by-nc/4.0/de
dc.subjectDFT calculationsen
dc.subjectNMR spectroscopyen
dc.subjectPhosphorus triorganodioxaphosphoraneen
dc.subjectX-ray diffractionen
dc.subject.ddc540
dc.subject.rswkDichtefunktionalformalismusde
dc.subject.rswkNMR-Spektroskopiede
dc.subject.rswkPhosphoranede
dc.subject.rswkRöntgenstreuungde
dc.titleChelating phosphorus–an O, C, O-coordinating pincer-type ligand coordinating PIII and PV centresen
dc.typeTextde
dc.type.publicationtypeResearchArticlede
dcterms.accessRightsopen access
eldorado.secondarypublicationtruede
eldorado.secondarypublication.primarycitationM. Gock, M. Lutter, A. Pintus, D. Schollmeier, M. Arca, V. Lippolis, K. Jurkschat, Chem. Eur. J. 2022, 28, e202201447.de
eldorado.secondarypublication.primaryidentifierhttps://doi.org/10.1002/chem.202201447de

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