Steric Influence on the Reactivity of Silyl-<i>o</i>-carboranes: Oxidative-Addition Reactions Involving Si−H and B−H Activation
作者:Young-Joo Lee、Jong-Dae Lee、Sung-Joon Kim、Jaejung Ko、Il-Hwan Suh、Minserk Cheong、Sang Ook Kang
DOI:10.1021/om034194d
日期:2004.1.1
(n = 1, R = Me, 1a; n = 1, R = Et, 1b; n = 2, R = Me, 3a; n = 2, R = Et, 3b) toward six-coordinate iridium [(Cp*IrCl2)2] and nine-coordinate rhenium [ReH7(PPh3)2] complexes has been investigated. Reactions between the mono(silyl)-o-carboranes (1a,b) and (Cp*IrCl2)2 resulted in the formation of four-membered, cyclic seven-coordinate iridium complexes Cp*IrH2[η1:η1-(SiR2)BC2B9H10-Si,B] (R = Me, 2a; R
单(甲硅烷基)-和双(甲硅烷基)-邻氨基甲酸酯(HSiR 2)n(C 2 B 10 H 12 - n)(n = 1,R = Me,1a ; n = 1,R = Et ,1b ; n = 2,R = Me,3a ; n = 2,R = Et,3b)向六配位铱[(Cp * IrCl 2)2 ]和九配位[[ReH 7(PPh 3)2 ]复合物已被调查。单(甲硅烷基)-o之间的反应-carboranes(1A,b)和(CP *的IrCl 2)2导致的形成四元,环状七坐标铱络合物的Cp * IRH 2 [η 1:η 1 - (SIR 2)BC 2乙9 ħ 10 -硅,B ](R = Me中,图2a ; R =的Et,2B),其中的Si-H活化,单(甲硅烷基) - ö -carborane(1)伴随着相邻的伴随B-H活化氢化硼。2a的X射线结构揭示铱中心以四脚钢琴凳的形式与硅和硼协调。在双之间的反应(甲硅烷基)