Ring Expansion of Cyclic Triplatinum(0) Silylene Complexes Induced by Insertion of Alkyne into a Si-Pt Bond
Ring Expansion of Cyclic Triplatinum(0) Silylene Complexes Induced by Insertion of Alkyne into a Si-Pt Bond
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炔插入 Si-Pt 键诱导环状三铂(0)硅撑配合物扩环
DOI：
10.1021/acs.organomet.5b00291
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发表时间：
2015
期刊：
影响因子：
2.8
通讯作者：
Kohtaro Osakada
中科院分区：
文献类型：
--
作者：
Kimiya Tanaka;Megumi Kamono;Makoto Tanabe;Kohtaro Osakada
具有桥联二芳基亚甲硅基配体的三角三铂(0)络合物，[{Pt(PMe3)}3(μ-SiAr2)3] (1: Ar = Ph,2: Ar = C6H4F-4)，与乙炔二甲酸二甲酯反应，得到新的 Pt3 络合物。络合物1与μ2-二苯基亚甲硅基和μ3-苯基(亚乙烯基)亚甲硅基配体进行等摩尔反应生成线性三铂配合物。后一种配体是通过双(二苯基甲硅烷基)乙烯配体的Ph基团的迁移形成的。 2与炔以1:3的摩尔比反应产生具有二硅铂环部分和Pt中心以及供体稳定的亚硅基配体的产物，并且它们被配位的炔分子分离。根据亚硅基配体的取代基，将具有二硅铂环戊烯基团的常见中间体转化为相应的三铂配合物。
Triangular triplatinum(0) complexes with bridging diarylsilylene ligands, [{Pt(PMe3)}3(μ-SiAr2)3] (1: Ar = Ph,2: Ar = C6H4F-4), reacted with dimethyl acetylenedicarboxylate to afford new Pt3complexes. The equimolar reaction of complex1produced a linear triplatinum complex with μ2-diphenylsilylene and μ3-phenyl(vinylene)silylene ligands. The latter ligand was formed via migration of a Ph group of the bis(diphenylsilyl)ethylene ligand. The reaction of2with 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.