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

18 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

Fingerprint

Iridium
Catalysis
Dimers
Oxidation
Catalysts
Stereoisomerism
Water
X ray crystallography
X Ray Crystallography
Silica Gel
Propionates
Silica gel
Chromatography
Isomers
Gel Chromatography
Carbon
Crystal structure
Metals
Ligands
Single crystals

ASJC Scopus subject areas

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

Cite this

Sharninghausen, L. S., Sinha, S. B., Shopov, D. Y., Choi, B., Mercado, B. Q., Roy, X., ... 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

High Oxidation State Iridium Mono-μ-oxo Dimers Related to Water Oxidation Catalysis. / Sharninghausen, Liam S.; Sinha, Shashi Bhushan; Shopov, Dimitar Y.; Choi, Bonnie; Mercado, Brandon Q.; Roy, Xavier; Balcells, David; Brudvig, Gary W; Crabtree, Robert H.

In: Journal of the American Chemical Society, Vol. 138, No. 49, 14.12.2016, p. 15917-15926.

Research output: Contribution to journalArticle

Sharninghausen, LS, Sinha, SB, Shopov, DY, Choi, B, Mercado, BQ, Roy, X, Balcells, D, Brudvig, GW & Crabtree, RH 2016, 'High Oxidation State Iridium Mono-μ-oxo Dimers Related to Water Oxidation Catalysis', Journal of the American Chemical Society, vol. 138, no. 49, pp. 15917-15926. https://doi.org/10.1021/jacs.6b07716
Sharninghausen LS, Sinha SB, Shopov DY, Choi B, Mercado BQ, Roy X et al. High Oxidation State Iridium Mono-μ-oxo Dimers Related to Water Oxidation Catalysis. Journal of the American Chemical Society. 2016 Dec 14;138(49):15917-15926. https://doi.org/10.1021/jacs.6b07716
Sharninghausen, Liam S. ; Sinha, Shashi Bhushan ; Shopov, Dimitar Y. ; Choi, Bonnie ; Mercado, Brandon Q. ; Roy, Xavier ; Balcells, David ; Brudvig, Gary W ; Crabtree, Robert H. / High Oxidation State Iridium Mono-μ-oxo Dimers Related to Water Oxidation Catalysis. In: Journal of the American Chemical Society. 2016 ; Vol. 138, No. 49. pp. 15917-15926.
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