Mononuclear ruthenium(II) complexes that catalyze water oxidation.
Two series of mononuclear ruthenium(II) complexes involving polypyridine-type ligands have been prepared, and their ability to act as catalysts for water oxidation has been examined. One series is of the type [Ru(tpy)(NN)Cl](PF(6)) (tpy = 2,2'; 6,2''-terpyridine), where NN is one of 12 different bidentate ligands, and the other series includes various combinations of 4-picoline, 2,2'-bipyridine (bpy), and tpy as well as the tetradentate 2,9-dipyrid-2'-yl-1,10-phenanthroline (dpp). The electronic absorption and redox data for these compounds have been measured and reported. The long-wavelength metal-to-ligand charge-transfer absorption and the first oxidation and reduction potentials are found to be consistent with the structure of the complex. Of the 23 complexes, 14 catalyze water oxidation and all of these contain a tpy or dpp. Kinetic measurements indicate a first-order reaction and together with a catalyst recovery experiment argue against the involvement of RuO(2). A tentative mechanism is proposed that involves a seven-coordinate Ru(VI)=O species that is attacked by water to form the critical O-O bond. Density functional theory calculations, which support the proposed mechanism, are performed.
Tseng
Huan-Wei
HW
Department of Chemistry, University of Houston, 136 Fleming Building, Houston, Texas 77204-5003, USA.
Zong
Ruifa
R
Muckerman
James T
JT
Thummel
Randolph
R