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Oxygen Evolution Catalyzed by a Mononuclear Ruthenium Complex Bearing Pendant SO 3 − Groups
Author(s) -
Yoshida Masaki,
Kondo Mio,
Torii Sena,
Sakai Ken,
Masaoka Shigeyuki
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201503365
Subject(s) - ruthenium , oxygen , catalysis , bearing (navigation) , chemistry , organic chemistry , physics , astronomy
Abstract Rational molecular design of catalytic systems capable of smooth OO bond formation is critical to the development of efficient catalysts for water oxidation. A new ruthenium complex was developed, which bears pendant SO 3 − groups in the secondary coordination sphere: [Ru(terpy)(bpyms)(OH 2 )] (terpy=2,2′:6′,2′′‐terpyridine, bpyms=2,2′‐bipyridine‐5,5′‐bis(methanesulfonate)). Water oxidation driven by a Ce 4+ oxidant is distinctly accelerated upon introduction of the pendant SO 3 − groups in comparisons to the parent catalyst, [Ru(terpy)(bpy)(OH 2 )] 2+ (bpy=2,2′‐bipyridine). Spectroscopic, electrochemical, and crystallographic investigations concluded that the pendant SO 3 − groups promote the formation of an OO bond via the secondary coordination sphere on the catalyst, whereas the influence of the pendant SO 3 − groups on the electronic structure of the [Ru(terpy)(bpy)(OH 2 )] 2+ core is negligible. The results of this work indicate that modification of the secondary coordination sphere is a valuable strategy for the design of water oxidation catalysts.