作者:M.F. Lappert、T.A. Nile、S. Takahashi
DOI:10.1016/s0022-328x(00)86392-5
日期:1974.6
Nio complex, its oxidative adduct L(diene)Ni(H)SiX3, a π-allyl complex L(π-allyl)NiSiX3, isomeric σ-pentenyl derivatives, and (I)-(III) + the Nio complex. Terminal acetylenes RC yield the products in which linear dimerisation accompanies hydrosilylation. The head-to-head adduct H2 CC(R)C(R)(SiX3 preponderates over the head-to-tail isomer R(H)C C(H)C(R)CH(SiX3); structures of the former were established
齐格勒型体系,例如M(acac)n -AlEt 3(M = Ni,Co或Fe)催化1,3-二烯或末端乙炔的氢化硅烷化。与异戊二烯或1,3-戊二烯的1,4-加成物CH 3 CHC(CH 3)CH 2的SiX 3或CH 3 CH 2 CH 2 CHCHCH 2的SiX 3是主要产物,和Ni盐[氯化镍2或Ni(acac)2 ]提供最佳的催化剂。为1,3-戊二烯和HSI(OR)3的副产物显著是CH 3 CHCHCH(SIX 3)CH 3,其形成通过添加膦而被抑制。与这些结果一致的链反应机理涉及依次形成Ni o配合物,其氧化加合物L(二烯)Ni(H)SiX 3,π-烯丙基配合物L(π-烯丙基)NiSiX 3,异构体σ-戊烯基衍生物和(I)-(III)+ Ni o配合物。末端乙炔RC 3产生线性二聚伴随氢化硅烷化的产物。的头-头加成物ħ 2 CC(R)C(R)(SIX 3个preponder