Activation of molecular oxygen, polyoxometalates, and liquid-phase catalytic oxidation

Research output: Contribution to journalArticle

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Abstract

In this Forum Article, we discuss the use of dioxygen (O2) in oxidations catalyzed by polyoxometalates. One- and two-electron-transfer oxidation of organic substrates is catalyzed by H5PV 2Mo10O40 and often occurs via an outer-sphere mechanism. The reduced polyoxometalate is reoxidized in a separate step by O2 with the formation of water. H5PV2Mo 10O40 also catalyzes electron transfer-oxygen transfer reactions. Here, in contrast to the paradigm that high-valent oxo species are often stronger oxygen-transfer species than lower-valent species, the opposite occurs. Thus, oxygen transfer from the catalyst is preceded by electron transfer from the organic substrate. The monooxygenase-type reduction of O2 with polyoxometalates is also discussed based on the formation of a stable iron(III) hydroperoxide compound that may have implications for the oxidation of other lower-valent polyoxometalates such as vanadium(IV)- and ruthenium(II)-substituted polyoxometalates. Finally, the formation of hybrid compounds through the attachment of electron-accepting polyoxometalates to coordination compounds can modify the reactivity of the latter by making higher-valent oxidation states more accessible.

Original languageEnglish
Pages (from-to)3594-3601
Number of pages8
JournalInorganic Chemistry
Volume49
Issue number8
DOIs
Publication statusPublished - Apr 19 2010

Fingerprint

Molecular oxygen
Catalytic oxidation
liquid phases
Chemical activation
activation
electron transfer
oxidation
Electrons
Oxygen
Liquids
oxygen
Oxidation
Vanadium
Ruthenium
vanadium
ruthenium
attachment
Substrates
Mixed Function Oxygenases
electrons

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Activation of molecular oxygen, polyoxometalates, and liquid-phase catalytic oxidation. / Neumann, Ronny.

In: Inorganic Chemistry, Vol. 49, No. 8, 19.04.2010, p. 3594-3601.

Research output: Contribution to journalArticle

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