Synthesis and Reactivity of Silyl Ruthenium Complexes: The Importance of Trans Effects in C−H Activation, Si−C Bond Formation, and Dehydrogenative Coupling of Silanes
作者:Vladimir K. Dioumaev、Leo J. Procopio、Patrick J. Carroll、Donald H. Berry
DOI:10.1021/ja035131p
日期:2003.7.1
complexes, cis-(PMe(3))(4)Ru(SiR(3))H (SiR(3) = SiMe(3), 1a; SiMe(2)CH(2)SiMe(3), 1b; SiEt(3), 1c; SiMe(2)H, 1d), has been synthesized by the reaction of hydrosilanes with (PMe(3))(3)Ru(eta(2)-CH(2)PMe(2))H (5), cis-(PMe(3))(4)RuMe(2) (6), or (PMe(3))(4)RuH(2) (9). Reaction with 6 proceeds via an intermediate product, cis-(PMe(3))(4)Ru(SiR(3))Me (SiR(3) = SiMe(3), 7a; SiMe(2)CH(2)SiMe(3), 7b). Alternatively
一系列八面体钌甲硅烷基氢化物配合物,cis-(PMe(3))(4)Ru(SiR(3))H (SiR(3) = SiMe(3), 1a; SiMe(2)CH(2)SiMe (3), 1b; SiEt(3), 1c; SiMe(2)H, 1d),是通过氢硅烷与 (PMe(3))(3)Ru(eta(2)-CH(2) )PMe(2))H (5)、顺式-(PMe(3))(4)RuMe(2) (6) 或 (PMe(3))(4)RuH(2) (9)。与 6 的反应通过中间产物 cis-(PMe(3))(4)Ru(SiR(3))Me (SiR(3) = SiMe(3), 7a; SiMe(2)CH(2)SiMe (3), 7b)。或者,1 和 7 已通过与另一种顺式-(PMe(3))(4)Ru(SiR(3))H 或顺式-(PMe(3))(4)Ru(SiR( 3))Me,以接近核磁共振时间尺度的速率发生。化合物