Reactions of Tungsten Acetylide-Silylene Complexes with Pyridines: Direct Observation of Silylene/Silyl Migration in Tungsten Acetylide and Carbyne/Vinylidene Frameworks
Reactions of Tungsten Acetylide-Silylene Complexes with Pyridines: Direct Observation of Silylene/Silyl Migration in Tungsten Acetylide and Carbyne/Vinylidene Frameworks
复制标题
乙炔钨-甲硅烷基配合物与吡啶的反应：乙炔钨和卡宾/亚乙烯基骨架中甲硅烷基/甲硅烷基迁移的直接观察
DOI：
10.1021/om300772c
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发表时间：
2012
期刊：
影响因子：
2.8
通讯作者：
坂場 裕之 ,尾池浩幸,新井康弘,權垠相
中科院分区：
文献类型：
--
作者：
西村 淳;樋口弘之;大和武彦;坂場 裕之 ,尾池浩幸,新井康弘,權垠相
乙酰基-硅基络合物Cp*(CO)2W(SiPh2)(CCtBu) （1a）与4-（二甲氨基）吡啶（DMAP）反应得到DMAP稳定的乙基硅基络合物-和顺式-Cp*(CO)2W(SiPh2·DMAP)(CCtBu)（反式-4和顺式-4）的平衡混合物。以Cp*(CO)2W(SiPh2)(CCSiMe3)(2)为主要反应产物Cp*(CO)2W[CC(SiPh2·DMAP)(SiMe3)] （6a）为主要反应产物，通过硅烯/硅基迁移与反式和顺式-Cp*(CO)2W(SiPh2·DMAP)(CCSiMe3)（反式-5aand顺式-5a）平衡。x射线晶体学揭示了顺式-4和6的新结构。2和吡啶的混合物表现出有趣的温度依赖性NMR光谱变化，表明在低温下形成反式和顺式-Cp*(CO)2W(SiPh2·py)(CCSiMe3) （trans-5bandcis-5b）和Cp*(CO)2W[CC(SiPh2·py)(SiMe3)] (6b)，而1和吡啶的混合物则没有这种光谱变化。
Reaction of acetylide–silylene complex Cp*(CO)2W(SiPh2)(CCtBu) (1a) with 4-(dimethylamino)pyridine (DMAP) gave an equilibrium mixture of DMAP-stabilized silylene acetylide complexestrans-andcis-Cp*(CO)2W(SiPh2·DMAP)(CCtBu) (trans-4andcis-4). The corresponding reaction using Cp*(CO)2W(SiPh2)(CCSiMe3) (2) produced the novel DMAP-coordinated silenylcarbyne/silylvinylidene complex Cp*(CO)2W[CC(SiPh2·DMAP)(SiMe3)] (6a) as a major product, which was equilibrated withtrans-andcis-Cp*(CO)2W(SiPh2·DMAP)(CCSiMe3) (trans-5aandcis-5a) via silylene/silyl migration. The novel structures ofcis-4and6awere revealed by X-ray crystallography. A mixture of2and pyridine exhibited interesting temperature-dependent NMR spectral changes, indicating the formation oftrans-andcis-Cp*(CO)2W(SiPh2·py)(CCSiMe3) (trans-5bandcis-5b) and Cp*(CO)2W[CC(SiPh2·py)(SiMe3)] (6b) at low temperature, while a mixture of1aand pyridine showed no such spectral changes.