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Reactivity of a cobalt(III)-peroxo complex in oxidative nucleophilic reactions
- Reactivity of a cobalt(III)-peroxo complex in oxidative nucleophilic reactions
- Jo Y.; Annaraj J.; Seo M.S.; Lee Y.-M.; Kim S.Y.; Cho J.; Nam W.
- Ewha Authors
- 남원우; 서미숙; 조재흥; 이용민
- SCOPUS Author ID
- 남원우; 이용민
- Issue Date
- Journal Title
- Journal of Inorganic Biochemistry
- vol. 102, no. 12, pp. 2155 - 2159
- SCI; SCIE; SCOPUS
- 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. © 2008 Elsevier Inc. All rights reserved.
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