☆ 4.7 Article

Probing Ligand Effects on O-O Bond Formation of Ru-Catalyzed Water Oxidation: A Computational Survey

INORGANIC CHEMISTRY (2014)

期刊

INORGANIC CHEMISTRY

卷 53, 期 14, 页码 7130-7136

出版社

AMER CHEMICAL SOC

DOI: 10.1021/ic500008c

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Chemistry, Inorganic & Nuclear

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National Natural Science Foundation of China [21290194, 21221002]
National Basic Research Program of China [2011CB808402]
Chinese Academy of Sciences
ISF grant [ISF 1183/13]

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Ligand effects of some representative monomeric Ru-based water oxidation catalysts on the key O-O formation step are revealed in this work. Three effects, namely, cis-effect, net charge effect, and steric hindrance effect, are identified, which can exert sizable modulation on the O-O formation barriers for the two widely accepted O-O formation mechanisms of WNA (water nucleophilic attack) and I2M (direct coupling of two high-valent metal oxo units). The study demonstrates that, through the way of ligand design, there remains a large space for improving O-O bond formation reactivity.

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