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

Research output: Contribution to journalArticle

18 Citations (Scopus)

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

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Chemical activation
activation
Oxygen
Oxidation
Cobalt
oxidation
Water
oxygen
cobalt
water
Atoms
Hydrogen bonds
Carbon
Sulfoxides
Phosphines
hydrogen bonds
epoxidation
Oxygenation
Epoxidation
carbon

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Dicobalt-μ-oxo polyoxometalate compound, [(α2-P 2W17O61Co)2O]14- : A potent species for water oxidation, C-H bond activation, and oxygen transfer. / Barats-Damatov, Delina; Shimon, Linda J W; Weiner, Lev; Schreiber, Roy E.; Jiménez-Lozano, Pablo; Poblet, Josep M.; De Graaf, Coen; Neumann, Ronny.

In: Inorganic Chemistry, Vol. 53, No. 3, 03.02.2014, p. 1779-1787.

Research output: Contribution to journalArticle

Barats-Damatov, D, Shimon, LJW, Weiner, L, Schreiber, RE, Jiménez-Lozano, P, Poblet, JM, 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, vol. 53, no. 3, pp. 1779-1787. https://doi.org/10.1021/ic402962c
Barats-Damatov, Delina ; Shimon, Linda J W ; Weiner, Lev ; Schreiber, Roy E. ; Jiménez-Lozano, Pablo ; Poblet, Josep M. ; De Graaf, Coen ; Neumann, Ronny. / Dicobalt-μ-oxo polyoxometalate compound, [(α2-P 2W17O61Co)2O]14- : A potent species for water oxidation, C-H bond activation, and oxygen transfer. In: Inorganic Chemistry. 2014 ; Vol. 53, No. 3. pp. 1779-1787.
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AU - Barats-Damatov, Delina

AU - Shimon, Linda J W

AU - Weiner, Lev

AU - Schreiber, Roy E.

AU - Jiménez-Lozano, Pablo

AU - Poblet, Josep M.

AU - De Graaf, Coen

AU - Neumann, Ronny

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AB - 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.

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