Mononuclear manganese-peroxo and bis(m-oxo)dimanganese complexes bearing a common N-methylated macrocyclic ligand

Hyeona Kang, Jaeheung Cho, Kyung Bin Cho, Takashi Nomura, Takashi Ogura, Wonwoo Nam

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34 Scopus citations

Abstract

Mononuclear MnIII-peroxo and dinuclear bis(μ-oxo)Mn III2 complexes that bear a common macrocyclic ligand were synthesized by controlling the concentration of the starting MnII complex in the reaction of H2O2 (i.e., a Mn III-peroxo complex at a low concentration (≤ 1 mM) and a bis(μ-oxo)MnIII2 complex at a high concentration (≥30mM)). These intermediates were successfully characterized by various physicochemical methods such as UV-visible spectroscopy, ESI-MS, resonance Raman, and X-ray analysis. The structural and spectroscopic characterization combined with density functional theory (DFT) calculations demon-strated unambiguously that the peroxo ligand is bound in a side-on fashion in the MnIII-peroxo complex and the Mn2O2 diamond core is in the bis(μ-oxo)MnIII2 complex. The reactivity of these intermediates was investigated in electrophilic and nucleophilic reactions, in which only the MnIII-peroxo complex showed a nucleophilic reactivity in the deformylation of aldehydes.

Original languageEnglish
Pages (from-to)14119-14125
Number of pages7
JournalChemistry - A European Journal
Volume19
Issue number42
DOIs
StatePublished - 11 Oct 2013

Keywords

  • Aldehyde deformylation
  • Bioinorganic chemistry
  • Kinetics
  • Manganese
  • Peroxo ligands

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