Dicobalt-μ-oxo polyoxometalate compound, [(α2-P 2W17O61Co)2O]14-: A potent species for water oxidation, C-H bond activation, and oxygen transfer

Delina Barats-Damatov, Linda J.W. Shimon, Lev Weiner, Roy E. Schreiber, Pablo Jiménez-Lozano, Josep M. Poblet, Coen De Graaf, Ronny Neumann

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Abstract

High-valent oxo compounds of transition metals are often implicated as active species in oxygenation of hydrocarbons through carbon-hydrogen bond activation or oxygen transfer and also in water oxidation. Recently, several examples of cobalt-catalyzed water oxidation have been reported, and cobalt(IV) species have been suggested as active intermediates. A reactive species, formally a dicobalt(IV)-μ-oxo polyoxometalate compound [(α2- P2W17O61Co)2O]14-, [(POMCo)2O], has now been isolated and characterized by the oxidation of a monomeric [α2-P2W17O 61CoII(H2O)]8-, [POMCo IIH2O], with ozone in water. The crystal structure shows a nearly linear Co-O-Co moiety with a Co-O bond length of ∼1.77 Å. In aqueous solution [(POMCo)2O] was identified by 31P NMR, Raman, and UV-vis spectroscopy. Reactivity studies showed that [(POMCo) 2O]2O] is an active compound for the oxidation of H 2O to O2, direct oxygen transfer to water-soluble sulfoxides and phosphines, indirect epoxidation of alkenes via a Mn porphyrin, and the selective oxidation of alcohols by carbon-hydrogen bond activation. The latter appears to occur via a hydrogen atom transfer mechanism. Density functional and CASSCF calculations strongly indicate that the electronic structure of [(POMCo)2O]2O] is best defined as a compound having two cobalt(III) atoms with two oxidized oxygen atoms.

Original languageEnglish
Pages (from-to)1779-1787
Number of pages9
JournalInorganic Chemistry
Volume53
Issue number3
DOIs
Publication statusPublished - Feb 3 2014

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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    Barats-Damatov, D., Shimon, L. J. W., Weiner, L., Schreiber, R. E., Jiménez-Lozano, P., Poblet, J. M., De Graaf, C., & Neumann, R. (2014). Dicobalt-μ-oxo polyoxometalate compound, [(α2-P 2W17O61Co)2O]14-: A potent species for water oxidation, C-H bond activation, and oxygen transfer. Inorganic Chemistry, 53(3), 1779-1787. https://doi.org/10.1021/ic402962c