Synthesis of η2-cyclooctene iridium and rhodium complexes supported by a novel P,N-chelate ligand and their reactivity toward hydrosilanes: facile Cl migration from metal to silicon via silylene complex intermediates and formation of a base-stabilised silylene complex
作者:Hisako Hashimoto、Toshinori Suzuki、Hiromi Tobita
DOI:10.1039/c0dt00264j
日期:——
chlorosilylene ligand (PcyN-P,N)2Ir2H2(μ-Cl)(μ-H)(μ-SiClMes) (5). The reaction of 1 with HSiMe2SiMes2Me occurred at room temperature to afford HSiMesMe2 and a silyl complex 6 formed by metallation of an ortho-methyl group of Mes, which slowly dimerised to give a dinuclear complex containing a chlorosilyl ligand (PcyN-P,N)2Ir2H(μ-Cl)(μ-H)[μ-SiMeCl(C6H3-2,4-Me2-6-CH)-Si,C,C] (7). The formation of complexes 5, 6
η 2 -Cyclooctene铱 和 铑带有P,N-螯合物C 6 H 3 Me-3-PCy 2 -4-NMe 2的配合物(缩写为P CY ñ), (P CY N- P,Ñ)的MC1(η 2 -COE)(1:M =铱,2:M =铑)的合成,并研究了对几种空间受阻的氢硅烷的反应,以阐明它们的反应性。的反应1用H 2 SIMES 2(MES =平庸 = 2,4,6-三甲基苯基)在40°C下进行铱络合物由氯亚甲硅烷基配体(P cy N- P,N)2 Ir 2 H 2(μ-Cl)(μ-H)(μ-SiClMes)桥接(5)。1与HSiMe 2 SiMes 2 Me的反应在室温下发生,得到HSiMesMe 2和由Mes的邻甲基金属化形成的甲硅烷基络合物6,缓慢地二聚生成含氯甲硅烷基配体的二核络合物(P cy N- P,N)2 Ir 2 H(μ-Cl)(μ-H)[μ-SiMeCl(C6 H 3 -2,4-Me