High Oxidation State Iridium Mono-μ-oxo Dimers Related to Water Oxidation Catalysis

Liam S. Sharninghausen, Shashi Bhushan Sinha, Dimitar Y. Shopov, Bonnie Choi, Brandon Q. Mercado, Xavier Roy, David Balcells, Gary W Brudvig, Robert H. Crabtree

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

The highly active iridium “blue solution” chemical and electrochemical water oxidation catalyst obtained from Cp*IrL(OH) precursors (L = 2-pyridyl-2-propanoate) has been difficult to characterize as no crystal structure can be obtained because of the multiplicity of geometrical isomers present. Other data suggest complete loss of the Cp* ligand and the formation of a LIr-O-IrL unit. We have now developed a route to a series of well-defined Ir(IV,IV) mono-μ-oxo dimers, containing the closely related L2Ir-O-IrL2 unit. Unlike the catalyst, these model compounds are separable by silica gel chromatography and readily form single crystals. We report three stereoisomers with the formula ClL2Ir-O-IrL2Cl, which are fully characterized, including by X-ray crystallography, and are compared to the “blue solution”. To the best of our knowledge, these species represent the first examples of structurally characterized dinuclear μ-oxo Ir(IV,IV) compounds without metal-carbon bonds.

Original languageEnglish
Pages (from-to)15917-15926
Number of pages10
JournalJournal of the American Chemical Society
Volume138
Issue number49
DOIs
Publication statusPublished - Dec 14 2016

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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    Sharninghausen, L. S., Sinha, S. B., Shopov, D. Y., Choi, B., Mercado, B. Q., Roy, X., Balcells, D., Brudvig, G. W., & Crabtree, R. H. (2016). High Oxidation State Iridium Mono-μ-oxo Dimers Related to Water Oxidation Catalysis. Journal of the American Chemical Society, 138(49), 15917-15926. https://doi.org/10.1021/jacs.6b07716