Novel 3-1-Silaallyl Tungsten Complexes via Si-H Bond Activation of Hydrovinylsilanes: Structure and Reactivity toward Metha
详细信息 查看全文
- 作者：Hiroyuki Sakaba ; Sanae Watanabe ; Chizuko Kabuto ; and Kuninobu Kabuto
- 刊名：Journal of the American Chemical Society
- 出版年：2003
- 出版时间：March 12, 2003
- 年：2003
- 卷：125
- 期：10
- 页码：2842 - 2843
- 全文大小：59K
- 年卷期：v.125,no.10(March 12, 2003)
- ISSN：1520-5126
文摘
Reactions of cis-Cp*(CO)2W(MeCN)Me (1) with HSiMe2(CH=CR2) (R = H, Me) afford the novel 
3-1-silaallyl complexes Cp*(CO)2W(3-Me2SiCHCR2) [R = H (2), Me (3)] accompanied by liberation of MeCN and CH4 via thermal Si-H bond activation. 3-Coordination and exo conformation of the 1-silaallyl ligand in 3 are shown by X-ray crystal analysis, which reveals the partial double bond character of the Si-C bond (1.800(4) Å) in the silaallyl moiety. Complexes 2 and 3 show extremely high reactivity toward MeOH to give the hydrido-(methoxysilyl)alkene complex trans-Cp*(CO)2WH(2-MeOMe2SiCH=CH2) (4) and the four-membered metallacycle Cp*(CO)2WCH(CHMe2)SiMe2 OMe (6), respectively.
3-1-silaallyl complexes Cp*(CO)2W(3-Me2SiCHCR2) [R = H (2), Me (3)] accompanied by liberation of MeCN and CH4 via thermal Si-H bond activation. 3-Coordination and exo conformation of the 1-silaallyl ligand in 3 are shown by X-ray crystal analysis, which reveals the partial double bond character of the Si-C bond (1.800(4) Å) in the silaallyl moiety. Complexes 2 and 3 show extremely high reactivity toward MeOH to give the hydrido-(methoxysilyl)alkene complex trans-Cp*(CO)2WH(2-MeOMe2SiCH=CH2) (4) and the four-membered metallacycle