A kinetic investigation of the oxidative addition reactions of the dimeric Bu4N[Ir2(μ-Dcbp)(cod)2] complex with iodomethane

被引：9

作者：

Grobbelaar, Ebeth ^{[1
]}

Purcell, Walter ^{[1
]}

Basson, Stephen S. ^{[1
]}

机构：

[1] Univ Free State, Dept Chem, ZA-9300 Bloemfontein, South Africa

来源：

INORGANICA CHIMICA ACTA | 2006年 / 359卷 / 12期

关键词：

oxidative addition; iridium; 3,5-dicarboxylatepyrazolate; iodomethane; kinetics;

D O I：

10.1016/j.ica.2006.03.041

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The kinetic results of the oxidative addition of iodomethane to Bu4N[Ir-2(mu-Dcbp)(cod)(2)] (Dcbp = 3,5-dicarboxylatepyrazolate anion) show that oxidative addition can occur via a direct equilibrium pathway (K-1 = 88(22) acetone, 51(3) 1,2-dichloroethane, 55(4) dichloromethane, 52(12) acetonitrile and 43(5) M-1 chloroform) or a solvent-assisted pathway (k(2), k(3)). Oxidative addition occurs mainly along the direct pathway, which is a factor 10-40 faster than the solvent-assisted pathway. The observed solvent effect cannot be attributed to the donosity or polarity of the solvents. The fairly negative Delta S-not equal value (-110(7)J K-1 mol(-1)) and the positive Delta H-not equal value (+47(2) kJ mol(-1)) for the oxidative addition step are indicative of an associative process. (c) 2006 Elsevier B.V. All rights reserved.

引用

页码：3800 / 3806

页数：7

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