Details

Autor(en) / Beteiligte

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

Titel

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

Ist Teil von

• Journal of inorganic biochemistry, 2008-12, Vol.102 (12), p.2155-2159

Ort / Verlag

United States: Elsevier Inc

Erscheinungsjahr

2008

Quelle

MEDLINE

Beschreibungen/Notizen

• A mononuclear cobalt(III)-peroxo complex bearing a macrocyclic tetradentate N 4 ligand, [Co III(TMC)(O 2)] + (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), was generated in the reaction of [Co II(TMC)] 2+ and H 2O 2 in the presence of triethylamine in CH 3CN. 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 [Fe III(TMC)(O 2)] + and [Mn III(TMC)(O 2)] +. In this reactivity comparison, the reactivities of metal-peroxo species were found to be in the order of [Mn III(TMC)(O 2)] + > [Co III(TMC)(O 2)] + > [Fe III(TMC)(O 2)] +. A positive Hammett ρ value of 1.8, obtained in the reactions of [Co III(TMC)(O 2)] + and para-substituted benzaldehydes, demonstrates that the aldehyde deformylation by the cobalt(III)-peroxo species occurs via a nucleophilic reaction.