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Cited by 386

The DOI matches its Crossref record; 27 of the 27 references it cites were found in a registry or an index.

Mononuclear Ruthenium(II) Complexes That Catalyze Water Oxidation

Tseng, Huan-Wei, Zong, Ruifa, Muckerman, James T., Thummel, Randolph·2008·Inorganic Chemistry

Abstract

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.

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Metadata

Authors
Tseng, H.-W., Zong, R., Muckerman, J. T., & Thummel, R.
Venue
Inorganic Chemistry
Published
2008-11-12
Volume
47
Issue
24
Pages
11763-11773
ISSN
  • 0020-1669 (ISSN-L)
  • 1520-510X
OpenAlex
W2007200392
Cited by
386
References
27
FWCI
20.81
Type
journal article
Language
en
Open access
closed

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