An iridium(IV) species, [Cp*Ir(NHC)Cl]+, related to a water-oxidation catalyst

Timothy P. Brewster, James D. Blakemore, Nathan D. Schley, Christopher D. Incarvito, Nilay Hazari, Gary W. Brudvig, Robert H. Crabtree

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Abstract

The Ir precatalyst (3) contains both a Cp* and a κ 2C2,C2′-1,3-diphenylimidazol-2-ylidene ligand, a C-C chelate, where one C donor is the NHC and the other is a cyclometalated N-phenyl wingtip group. The structure of 3 was confirmed by X-ray crystallography. Like our other recently described Cp*Ir catalysts, this compound is a precursor to a catalyst that can oxidize water to dioxygen. Electrochemical characterization of the new compound shows that it has a stable iridium(IV) oxidation state, [Cp*IrIV(NHC)Cl]+, in contrast with the unstable Ir(IV) state seen in our previous cyclometalated [Cp*IrIII(2-pyridyl-2′-phenyl)Cl] catalyst. The new iridium(IV) species has been characterized by EPR spectroscopy and has a rhombic symmetry, a consequence of the ligand environment. These results both support previous studies which suggest that Cp*Ir catalysts can be advanced through the relevant catalytic cycle(s) in one-electron steps and help clarify the electrochemical behavior of this class of water-oxidation catalysts.

Original languageEnglish
Pages (from-to)965-973
Number of pages9
JournalOrganometallics
Volume30
Issue number5
DOIs
Publication statusPublished - Mar 14 2011

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Brewster, T. P., Blakemore, J. D., Schley, N. D., Incarvito, C. D., Hazari, N., Brudvig, G. W., & Crabtree, R. H. (2011). An iridium(IV) species, [Cp*Ir(NHC)Cl]+, related to a water-oxidation catalyst. Organometallics, 30(5), 965-973. https://doi.org/10.1021/om101016s