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Mononuclear Manganese-Peroxo and Bis(mu-oxo)dimanganese Complexes Bearing a Common N-Methylated Macrocyclic Ligand

Title
Mononuclear Manganese-Peroxo and Bis(mu-oxo)dimanganese Complexes Bearing a Common N-Methylated Macrocyclic Ligand
Authors
Kang, H[Kang, Hyeona]Cho, J[Cho, Jaeheung]Cho, KB[Cho, Kyung-Bin]Nomura, T[Nomura, Takashi]Ogura, T[Ogura, Takashi]Nam, W[Nam, Wonwoo]
DGIST Authors
Cho, J[Cho, Jaeheung]
Issue Date
2013-10-11
Citation
Chemistry: A European Journal, 19(42), 14119-14125
Type
Article
Article Type
Article
Keywords
Aldehyde DeformylationAldehydesBiochemistryBioinorganic ChemistryEnzyme KineticsKineticsLigandsMacro-Cyclic LigandsManganeseNucleophilic ReactionNucleophilic ReactivityPeroxo LigandsPhysicochemical MethodsSpectroscopic CharacterizationSynthesis (Chemical)Ultraviolet Visible SpectroscopyUV-Visible Spectroscopy
ISSN
0947-6539
Abstract
Mononuclear MnIII-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 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)MnIII 2 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)MnIII 2 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. © 2013 Wiley-VCH Verlag GmbH & Co. KGaA.
URI
http://hdl.handle.net/20.500.11750/3189
DOI
10.1002/chem.201301641
Publisher
Wiley-VCH Verlag
Files:
There are no files associated with this item.
Collection:
Emerging Materials ScienceETC1. Journal Articles


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