Mechanism of water oxidation by single-site ruthenium complex catalysts.
The mechanism of Ce(IV) water oxidation catalyzed by [Ru(tpy)(bpm)(OH(2))](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.
Concepcion
Javier J
JJ
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, USA.
Tsai
Ming-Kang
MK
Muckerman
James T
JT
Meyer
Thomas J
TJ
D002384:Catalysis; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D017975:Ruthenium Compounds / Q000737:chemistry*; D013053:Spectrophotometry; D014867:Water / Q000737:chemistry*
D017975:Ruthenium Compounds; D014867:Water; D010100:Oxygen