Mechanism of Water Oxidation by Single-Site Ruthenium Complex Catalysts

被引：420

作者：

Concepcion, Javier J. ^{[1
]}

Tsai, Ming-Kang ^{[2
]}

Muckerman, James T. ^{[2
]}

Meyer, Thomas J. ^{[1
]}

机构：

[1] Univ N Carolina, Dept Chem, Chapel Hill, NC 27599 USA

[2] Brookhaven Natl Lab, Dept Chem, Upton, NY 11973 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2010年 / 132卷 / 05期

关键词：

MOLECULAR-OXYGEN; IONIC-SOLUTIONS; PHOTOSYSTEM-II; DIOXYGEN; REACTIVITY; HYDROPEROXO; INSERTION; FAMILY; OSMIUM; REDOX;

D O I：

10.1021/ja904906v

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The mechanism of Ce(IV) water oxidation catalyzed by [Ru(tpy)(bpm)(OH2)](2+) (tpy = 2,2':6',2 ''-terpyridine; bpm = 2,2'-bipyrimidine) and related single-site catalysts has been determined by a combination of mixing and stopped-flow experiments with spectrophotometric monitoring. The mechanism features O---O coupling by water attack on Ru-V=O3+ and three peroxidic intermediates that have been characterized by a combination of spectroscopy and DFT calculations.

引用

页码：1545 / 1557

页数：13

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