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Mononuclear Manganese–Peroxo and Bis(μ‐oxo)dimanganese Complexes Bearing a Common N‐Methylated Macrocyclic Ligand
Author(s) -
Kang Hyeona,
Cho Jaeheung,
Cho KyungBin,
Nomura Takashi,
Ogura Takashi,
Nam Wonwoo
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201301641
Subject(s) - reactivity (psychology) , chemistry , ligand (biochemistry) , nucleophile , manganese , electrophile , resonance (particle physics) , polymer chemistry , medicinal chemistry , photochemistry , crystallography , catalysis , organic chemistry , medicine , biochemistry , physics , receptor , alternative medicine , pathology , particle physics
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 H 2 O 2 (i.e., a Mn III –peroxo complex at a low concentration (≤1 m M ) and a bis(μ‐oxo)Mn III 2 complex at a high concentration (≥30 m M )). 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 Mn 2 O 2 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.