Homogeneous Isomerization of 1-Butene Catalyzed by [MX<sub>2</sub>(PR<sub>3</sub>)<sub>2</sub>]–NaBH<sub>4</sub>Systems (M=Co, Ni, X=Halides, SCN, PR<sub>3</sub>=PPh<i><sub>n</sub></i>Et<sub>3−<i>n</i></sub>)<sup>−</sup>Acceleration by Phosphine Addition and Stereoselectivity
作者:Hiroyoshi Kanai、Shigeyoshi Sakaki、Takenobu Sakatani
DOI:10.1246/bcsj.60.1589
日期:1987.5
stoichiometric or a little excess amount of NaBH4 was treated with [MX2(PR3)2] (M=Co, Ni, X= halides, SCN, PR3=PPhnEt3−n) in THF–1,2-dimethoxyethane to form monohydride species which were active for isomerization of 1-butene. The reaction was accelerated by excess PPh3 in [CoX2(PPh3)2]–NaBH4 systems. Other catalytic systems have optimum ratios of excess phosphine to metal for getting maximum activities. Thiocyanate–metal
用 [MX2(PR3)2] (M=Co, Ni, X= 卤化物, SCN, PR3=PPhnEt3−n) 在 THF-1,2-二甲氧基乙烷中处理化学计量或稍微过量的 NaBH4 以形成一氢化物对 1-丁烯的异构化有活性。[CoX2(PPh3)2]-NaBH4 系统中过量的 PPh3 加速了反应。其他催化系统具有过量膦与金属的最佳比例以获得最大活性。硫氰酸盐-金属配合物在每个 Co-和 Ni-催化剂体系中都是最活跃的。顺式选择性取决于 PR3 的锥角、阴离子配体的大小和复合物的拥挤结构。