New water oxidation chemistry of a seven-coordinate ruthenium complex with a tetradentate polypyridyl ligand

James Muckerman, Marta Kowalczyk, Yosra M. Badiei, Dmitry Polyansky, Javier J. Concepcion, Ruifa Zong, Randolph P. Thummel, Etsuko Fujita

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Abstract

The mononuclear ruthenium(II) complex [Ru]2+ (Ru = Ru(dpp)(pic)2, where dpp is the tetradentate 2,9-dipyrid-2′-yl- 1,10-phenanthroline ligand and pic is 4-picoline) reported by Thummel's group (Inorg. Chem. 2008, 47, 1835-1848) that contains no water molecule in its primary coordination shell is evaluated as a catalyst for water oxidation in artificial photosynthesis. A detailed theoretical characterization of the energetics, thermochemistry, and spectroscopic properties of intermediates allowed us to interpret new electrochemical and spectroscopic experimental data, and propose a mechanism for the water oxidation process that involves an unprecedented sequence of seven-coordinate ruthenium complexes as intermediates. This analysis provides insights into a mechanism that generates four electrons and four protons in the solution and a gas-phase oxygen molecule at different pH values. On the basis of the calculations and corroborated substantially by experiments, the catalytic cycle goes through [2Ru III]3+ and [2RuV(O)]3+ to [1RuIV(OOH)]3+ then [2Ru III(···3O2)]3+ at pH 0, and through [3RuIV(O)]2+, [ 2RuV(O)]3+, and [1Ru IV(OO)]2+ at pH 9 before reaching the same [ 2RuIII(···3O 2)]3+ species, from which the liberation of the weakly bound O2 might require an additional oxidation to form [ 3RuIV(O)]2+ to initiate further cycles involving all seven-coordinate species.

Original languageEnglish
Pages (from-to)6904-6913
Number of pages10
JournalInorganic Chemistry
Volume53
Issue number13
DOIs
Publication statusPublished - Jul 7 2014

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Ruthenium
ruthenium
chemistry
Ligands
Oxidation
ligands
oxidation
Water
Picolines
water
Thermochemistry
cycles
Molecules
photosynthesis
Photosynthesis
thermochemistry
Protons
molecules
Gases
vapor phases

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

New water oxidation chemistry of a seven-coordinate ruthenium complex with a tetradentate polypyridyl ligand. / Muckerman, James; Kowalczyk, Marta; Badiei, Yosra M.; Polyansky, Dmitry; Concepcion, Javier J.; Zong, Ruifa; Thummel, Randolph P.; Fujita, Etsuko.

In: Inorganic Chemistry, Vol. 53, No. 13, 07.07.2014, p. 6904-6913.

Research output: Contribution to journalArticle

Muckerman, James ; Kowalczyk, Marta ; Badiei, Yosra M. ; Polyansky, Dmitry ; Concepcion, Javier J. ; Zong, Ruifa ; Thummel, Randolph P. ; Fujita, Etsuko. / New water oxidation chemistry of a seven-coordinate ruthenium complex with a tetradentate polypyridyl ligand. In: Inorganic Chemistry. 2014 ; Vol. 53, No. 13. pp. 6904-6913.
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