title: Mononuclear manganese-peroxo and bis(μ-oxo)dimanganese complexes bearing a common N-methylated macrocyclic ligand.
abstract: Mononuclear Mn(III) -peroxo and dinuclear bis(μ-oxo)Mn(III) 2 complexes that bear a common macrocyclic ligand were synthesized by controlling the concentration of the starting Mn(II) complex in the reaction of H2 O2 (i.e., a Mn(III) -peroxo complex at a low concentration (≤1 mM) and a bis(μ-oxo)Mn(III) 2 complex at a high concentration (≥30 mM)). 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 demonstrated unambiguously that the peroxo ligand is bound in a side-on fashion in the Mn(III) -peroxo complex and the Mn2 O2 diamond core is in the bis(μ-oxo)Mn(III) 2 complex. The reactivity of these intermediates was investigated in electrophilic and nucleophilic reactions, in which only the Mn(III) -peroxo complex showed a nucleophilic reactivity in the deformylation of aldehydes.
authors.affiliation: Department of Bioinspired Science, Department of Chemistry and Nano Science, Ewha Womans University, Seoul 120-750 (Korea).
authors.forename: Hyeona
authors.initials: H
authors.lastname: Kang
authors.forename: Jaeheung
authors.initials: J
authors.lastname: Cho
authors.forename: Kyung-Bin
authors.initials: KB
authors.lastname: Cho
authors.forename: Takashi
authors.initials: T
authors.lastname: Nomura
authors.forename: Takashi
authors.initials: T
authors.lastname: Ogura
authors.forename: Wonwoo
authors.initials: W
authors.lastname: Nam
mesh_terms: D018360:Crystallography, X-Ray; D008024:Ligands; D047028:Macrocyclic Compounds / Q000737:chemistry*; D008345:Manganese / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*
chemical_list: D008024:Ligands; D047028:Macrocyclic Compounds; D009942:Organometallic Compounds; D008345:Manganese
keywords: aldehyde deformylation; bioinorganic chemistry; kinetics; manganese; peroxo ligands