Formation, Characterization, and O-O Bond Activation of a Peroxomanganese(III) Complex Supported by a Cross-Clamped Cyclam Ligand.
作者： Hannah E. Colmer , Anthony W. Howcroft , Timothy A. Jackson
DOI: 10.1021/ACS.INORGCHEM.5B02398
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摘要: Although there have been reports describing the nucleophilic reactivity of peroxomanganese(III) intermediates, as well their conversion to high-valent oxo-bridged dimers, it remains a challenge activate species for high-valent, mononuclear manganese complexes. Herein, we report generation, characterization, and activation adduct supported by cross-clamped, macrocyclic Me2EBC ligand (4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane). This is known support MnIV with well-defined spectroscopic properties, which provides an opportunity identify products from O–O bond corresponding MnIII–peroxo adduct. The intermediate, [MnIII(O2)(Me2EBC)]+, was prepared at low-temperature addition KO2 [MnII(Cl)2(Me2EBC)] in CH2Cl2, this complex characterized electronic absorption, electron paramagnetic resonance (EPR), an...
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