Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, USA.
J Am Chem Soc. 2010 Feb 10;132(5):1545-57. doi: 10.1021/ja904906v.
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.
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。
