Reactivity of a cobalt(III)-peroxo complex in oxidative nucleophilic reactions

Youngrae Jo, Jamespandi Annaraj, Mi Sook Seo, Yong Min Lee, Sung Yeon Kim, Jaeheung Cho, Wonwoo Nam

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43 Scopus citations

Abstract

A mononuclear cobalt(III)-peroxo complex bearing a macrocyclic tetradentate N4 ligand, [CoIII(TMC)(O2)]+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), was generated in the reaction of [CoII(TMC)]2+ and H2O2 in the presence of triethylamine in CH3CN. The reactivity of the cobalt(III)-peroxo complex was investigated in aldehyde deformylation with various aldehydes and compared with that of iron(III)- and manganese(III)-peroxo complexes, such as [FeIII(TMC)(O2)]+ and [MnIII(TMC)(O2)]+. In this reactivity comparison, the reactivities of metal-peroxo species were found to be in the order of [MnIII(TMC)(O2)]+ > [CoIII(TMC)(O2)]+ > [FeIII(TMC)(O2)]+. A positive Hammett ρ value of 1.8, obtained in the reactions of [CoIII(TMC)(O2)]+ and para-substituted benzaldehydes, demonstrates that the aldehyde deformylation by the cobalt(III)-peroxo species occurs via a nucleophilic reaction.

Original languageEnglish
Pages (from-to)2155-2159
Number of pages5
JournalJournal of Inorganic Biochemistry
Volume102
Issue number12
DOIs
StatePublished - Dec 2008

Keywords

  • Aldehyde deformylation
  • Bioinorganic chemistry
  • Cobalt-peroxo
  • O-O activation
  • Oxidation

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