891486-24-1Relevant articles and documents
Spectroscopic and reactivity studies of platinum-silicon monomers and dimers
Braddock-Wilking, Janet,Corey, Joyce Y.,Trankler, Kevin A.,Xu, Huan,French, Lisa M.,Praingam, Ngamjit,White, Colin,Rath, Nigam P.
, p. 2859 - 2871 (2008/10/09)
Mononuclear Pt-Si-containing complexes with the general formulas (Ph 3P)2Pt(H)(SiAr2H) and (Ph3P) 2-Pt(SiAr2H)2 were produced at low temperature from the reaction of the secondary arylhydrosilanes Ph2-SiH 2, C12H8SiH2 (silafluorene), and C20H24SiH2 (3,7-di-tert-butylsilafluorene) with (Ph3P)2Pt(η2-C2H4). When solutions of the mononuclear complexes were run at low temperature and then warmed to room temperature, or when the reactions were run at room temperature or above, dinuclear Pt-Si-containing complexes were produced, [(Ph 3P)Pt(μ-η2-HSiAr2)]2 (Ar = Ph (4)) and [(Ph3P)2Pt(H)(μ-SiAr2)(μ- η2-HSiAr2)Pt(PPh3)] (Ar2 = C12H8 (8), C20H24 (15); both fluxional). A mechanism is proposed for the formation of the unsymmetrical dinuclear complexes (8 and 15) that involves a bimolecular reaction between two mononuclear species, (Ph3P)2Pt(H)(SiAr2H) and (Ph3P)Pt(H)(SiAr2H). VT-NMR studies of complexes 8 and 15 illustrate that a fluxional process occurs which can be explained by elimination and recoordination of a PPh3 ligand. Complex 15 reacted with added P(p-Tol)3 to produce a mixture of dinuclear products consistent with the presence of both types of phosphines in the dinuclear complexes. Reaction of the dinuclear complex 8 with the mononuclear complex 16 as well as the elevated-temperature reaction between 8 and 15 will be described.
