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单原子钌配合物催化剂水氧化机制。

Mechanism of water oxidation by single-site ruthenium complex catalysts.

机构信息

Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, USA.

出版信息

J Am Chem Soc. 2010 Feb 10;132(5):1545-57. doi: 10.1021/ja904906v.

Abstract

The mechanism of Ce(IV) water oxidation catalyzed by Ru(tpy)(bpm)(OH(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)=O(3+) and three peroxidic intermediates that have been characterized by a combination of spectroscopy and DFT calculations.

摘要

Ru(tpy)(bpm)(OH(2))(tpy = 2,2':6',2''-三联吡啶;bpm = 2,2'-联嘧啶)和相关的单原子催化剂催化 Ce(IV)水氧化的机理已通过混合和停流实验与分光光度监测相结合来确定。该机理的特征在于 Ru(V)=O(3+)和三个过氧中间体的 O---O 偶联,这些中间体已通过光谱和 DFT 计算相结合进行了表征。

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