Oxidative catalysis by Mn4O4 6+ cubane complexes

Thomas G. Carrell, Shari Cohen, G Charles Dismukes

Research output: Contribution to journalArticle

58 Citations (Scopus)

Abstract

The oxidation of a variety of substrates (thioethers, hydrocarbons, alkenes, benyzl alcohol and benzaldehyde) by tBuOOH catalyzed by Mn4O4(O2PPh2)6 (1) and Mn4O4(O2P(p-MePh)2)6 (2) is reported. These reactions illustrate the first examples of oxidative catalysis using a manganese-oxo complex with a Mn4O4 cubane core. These uncharged complexes contain Mn ions in a mixed valence oxidation state, formally Mn4(2III, 2IV), and are bridged by bulky diphenylphosphinate chelates across each of the six faces of the cube. Using this system, methyl phenyl sulfide is selectively mono-oxygenated to methyl phenyl sulfoxide with high catalytic efficiency, and no evidence for further oxidation to the thermodynamically preferred sulfone. Toluene is oxidized to a mixture of benzyl alcohol, benzaldehyde, and benzoic acid with high catalytic efficiencies. Lower catalytic efficiencies are observed in the oxidation of styrene to a mixture of styrene oxide and benzaldehyde, of cyclohexene to a mixture of cyclohexene oxide, 2-cyclohexen-1-ol, and 2-cyclohexen-1-one, and of cyclohexane to a mixture of cyclohexanol and cyclohexanone. The observed product distribution from the oxidation of hydrocarbons has the characteristics of a free radical-based oxidation mechanism. However, the sulfoxidation and epoxidation activity of the 1/tBuOOH system, as well as the observed steric preferences for less congested substrates, suggest that a metal-oxo centered oxidation mechanism is active in the reactions studied here. An intermediate species, characterized by a UV-VIS band centered at 610 nm is observed in all reaction mixtures, and forms upon reaction of 1 or 2 with tBuOOH. Preliminary evidence suggests this reactive intermediate may correspond to a Mn(V)=O species. Kinetic studies suggest two pathways for oxidation: one involving an oxygen atom transfer (two-electron branch), and the other involving a hydrogen atom abstraction (one-electron branch).

Original languageEnglish
Pages (from-to)3-15
Number of pages13
JournalJournal of Molecular Catalysis A: Chemical
Volume187
Issue number1
DOIs
Publication statusPublished - Sep 9 2002

Keywords

  • Alkyl hydroperoxides
  • Oxidation
  • Polynuclear manganese complexes

ASJC Scopus subject areas

  • Catalysis
  • Process Chemistry and Technology

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