28986-19-8Relevant academic research and scientific papers
Thermolysis reactions of cis-PtR(SiPh3)(PMe2Ph)2 in solution
Hasebe, Koh,Kamite, Jun,Mori, Takuya,Katayama, Hiroyuki,Ozawa, Fumiyuki
, p. 2022 - 2030 (2008/10/08)
A series of trans- and cis-PtR(SiPh3)(PMe2Ph)2 complexes have been prepared and their thermolysis reactions in solution examined. The trans isomers (R = Me, Et) are robust, and only the methyl complex affords MeSiPh3 as the reductive elimination product in 72-82% yields. In contrast, the cis isomers (R = Me, Et, Pr, Bu) form the corresponding alkylsilanes in almost quantitative yields (>97%). Despite the selective formation of the reductive elimination products, the cis-alkyl-silyl complexes bearing β-hydrogens undergo a rapid repetition of the β-hydrogen elimination and insertion processes, as confirmed by a deuterium-labeling experiment using cis-Pt(CH2CD3)(SiPh3)(PMe2Ph) 2. The alkylsilane formation from the cis isomers proceeds via two reaction paths. One is the direct C-Si reductive elimination. On the other path, the cis-PtR(SiPh3)(PMe2Ph)2 complexes are initially isomerized to the corresponding cis-PtPh(SiRPh2)(PMe2Ph)2 complexes by the exchange of the Pt-R group with the Si-Ph group, and the resulting phenyl-silyl complexes reductively eliminate alkylsilanes. The methyl-silyl complex decomposes exclusively by the former path, while the other alkyl-silyl complexes (R = Et, Pr, Bu) follow mainly the latter path. Preparation and thermolysis reaction of the related cis-PtEt(GePh3)(PMe2Ph)2 are also reported.
