The First Alkene−Platinum−Silyl Complexes: Lifting the Hydrosilation Mechanism Shroud with Long-Lived Precatalytic Intermediates and True Pt Catalysts
作者:Aroop K. Roy、Richard B. Taylor
DOI:10.1021/ja0127335
日期:2002.8.1
The synthesis, characterization, and exploratory chemistry of two classes of alkene-platinum-silyl complexes, which have been postulated as hydrosilation intermediates, are described in this report. The unique dimeric complexes 1, [R(3)Si(mu-Cl)(eta(2)-COD)Pt](2) [R(3)Si = Et(3)Si, MeCl(2)Si, Me(2)ClSi, "(EtO)(3)Si", PhMe(2)Si, and (Me(3)SiO)Me(2)Si; COD = cycloocta-1,5-diene], and the bis-silyl complexes
本报告描述了两类烯烃-铂-甲硅烷基复合物的合成、表征和探索性化学,它们被假定为氢化硅烷化中间体。独特的二聚体配合物 1, [R(3)Si(mu-Cl)(eta(2)-COD)Pt](2) [R(3)Si = Et(3)Si, MeCl(2)Si, Me (2)ClSi、“(EtO)(3)Si”、PhMe(2)Si和(Me(3)SiO)Me(2)Si;COD = cycloocta-1,5-diene], 和双甲硅烷基复合物 2, (eta(4)-COD)Pt(SiR(3))(2) (R(3)Si = Cl(3)Si, MeCl(2)Si、Me(2)ClSi 和 PhMe(2)Si) 分别由 2 和 4 当量的相应氢硅烷与 Pt(COD)Cl(2) 在存在下的顺序反应形成少量过量的 COD。配合物 1 在室温下可在溶液中稳定许多天,但会通过氯硅烷的缓慢消除而分解。一些双甲硅烷基化合物 2 在惰性气氛下,尤其是在