Ring Expansion of Cyclic Triplatinum(0) Silylene Complexes Induced by Insertion of Alkyne into a Si鈥揚t Bond

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• 作者：Kimiya Tanaka ; Megumi Kamono ; Makoto Tanabe ; Kohtaro Osakada
• 刊名：Organometallics
• 出版年：2015
• 出版时间：June 22, 2015
• 年：2015
• 卷：34
• 期：12
• 页码：2985-2990
• 全文大小：373K
• ISSN：1520-6041

文摘

Triangular triplatinum(0) complexes with bridging diarylsilylene ligands, [{Pt(PMe₃)}₃(渭-SiAr₂)₃] (1: Ar = Ph, 2: Ar = C₆H₄F-4), reacted with dimethyl acetylenedicarboxylate to afford new Pt₃ complexes. The equimolar reaction of complex 1 produced a linear triplatinum complex with 渭₂-diphenylsilylene and 渭₃-phenyl(vinylene)silylene ligands. The latter ligand was formed via migration of a Ph group of the bis(diphenylsilyl)ethylene ligand. The reaction of 2 with the alkyne in a 1:3 molar ratio yielded the product having a disilaplatinacyclic moiety and a Pt center with the donor-stabilized silylene ligand, and they were separated by the coordinated alkyne molecule. A common intermediate having a disilaplatinacyclopentene group was converted into the respective triplatinum complexes, depending on the substituents of the silylene ligand.