DYNAMICAL INVESTIGATIONS OF THE CATALYTIC MECHANISMS OF WATER OXIDATION BY THE [(BPY)(2)RU(OH2)]2O(4+) ION

被引：34

作者：

LEI, YB ^{[1
]}

HURST, JK ^{[1
]}

机构：

[1] OREGON GRAD INST SCI & TECHNOL, DEPT CHEM BIOCHEM & MOLEC BIOL, PORTLAND, OR 97291 USA

来源：

INORGANICA CHIMICA ACTA | 1994年 / 226卷 / 1-2期

关键词：

KINETICS AND MECHANISM; CATALYSIS; WATER OXIDATION; RUTHENIUM COMPLEXES; BIDENTATE LIGAND COMPLEXES; OXO COMPLEXES;

D O I：

10.1016/0020-1693(94)04085-0

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Steady-state kinetic methods have been applied to the study of (mu-oxo)bis[cis-aquabis(2,2'-bipyridine)ruthenium(III)] ion-catalyzed water oxidation by the Co3+ ion. Initial rates of O-2 evolution exhibited first-order dependence upon the catalyst concentration, indicating that the catalytic cycle involves a single mu-oxo ion. The rate dependence upon Co3+ and Co2+ concentrations was complex, but consistent only with dimeric ions in the Ru2O [5,5] or higher oxidation states being the O-2-releasing species. These data are consistent with our previously proposed mechanistic model in which a significant component of catalysis is activation of solvent water by hydrogen bonding to the bridging mu-oxo atom.

引用

页码：179 / 185

页数：7