Water oxidation with mononuclear ruthenium(II) polypyridine complexes involving a direct RuIV = O pathway in neutral and alkaline media

Yosra M. Badiei, Dmitry Polyansky, James Muckerman, David J. Szalda, Rubabe Haberdar, Ruifa Zong, Randolph P. Thummel, Etsuko Fujita

Research output: Contribution to journalArticle

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Abstract

The catalytic water oxidation mechanism proposed for many single-site ruthenium complexes proceeds via the nucleophilic attack of a water molecule on the RuV =O species. In contrast, Ru(II) complexes containing 4-t-butyl-2,6-di-1′,8′-(naphthyrid-2′-yl)-pyridine (and its bisbenzo-derivative), an equatorial water, and two axial 4-picolines follow the thermodynamically more favorable "direct pathway" via [RuIV =O]2+, which avoids the higher oxidation state [RuV =O]3+ in neutral and basic media. Our experimental and theoretical results that focus on the pH-dependent onset catalytic potentials indicative of a PCET driven low-energy pathway for the formation of products with an O-O bond (such as [RuIII-OOH]2+ and [RuIV-OO] 2+) at an applied potential below the RuV =O/Ru IV =O couple clearly support such a mechanism. However, in the cases of [Ru(tpy)(bpy)(OH2)]2+ and [Ru(tpy)(bpm)(OH 2)]2+, the formation of the RuV =O species appears to be required before O-O bond formation. The complexes under discussion provide a unique functional model for water oxidation that proceeds by four consecutive PCET steps in neutral and alkaline media.

Original languageEnglish
Pages (from-to)8845-8850
Number of pages6
JournalInorganic Chemistry
Volume52
Issue number15
DOIs
Publication statusPublished - Aug 5 2013

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Ruthenium
ruthenium
Oxidation
oxidation
Water
water
Picolines
attack
pyridines
Derivatives
Molecules
products
molecules
energy

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Water oxidation with mononuclear ruthenium(II) polypyridine complexes involving a direct RuIV = O pathway in neutral and alkaline media. / Badiei, Yosra M.; Polyansky, Dmitry; Muckerman, James; Szalda, David J.; Haberdar, Rubabe; Zong, Ruifa; Thummel, Randolph P.; Fujita, Etsuko.

In: Inorganic Chemistry, Vol. 52, No. 15, 05.08.2013, p. 8845-8850.

Research output: Contribution to journalArticle

Badiei, Yosra M. ; Polyansky, Dmitry ; Muckerman, James ; Szalda, David J. ; Haberdar, Rubabe ; Zong, Ruifa ; Thummel, Randolph P. ; Fujita, Etsuko. / Water oxidation with mononuclear ruthenium(II) polypyridine complexes involving a direct RuIV = O pathway in neutral and alkaline media. In: Inorganic Chemistry. 2013 ; Vol. 52, No. 15. pp. 8845-8850.
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