Formation, Characterization, and O-O Bond Activation of a Peroxomanganese(III) Complex Supported by a Cross-Clamped Cyclam Ligand

Inorganic Chemistry
Hannah E ColmerTimothy A Jackson

Abstract

Although there have been reports describing the nucleophilic reactivity of peroxomanganese(III) intermediates, as well as their conversion to high-valent oxo-bridged dimers, it remains a challenge to activate peroxomanganese(III) species for conversion to high-valent, mononuclear manganese complexes. Herein, we report the generation, characterization, and activation of a peroxomanganese(III) adduct supported by the cross-clamped, macrocyclic Me2EBC ligand (4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane). This ligand is known to support high-valent, mononuclear Mn(IV) species with well-defined spectroscopic properties, which provides an opportunity to identify mononuclear Mn(IV) products from O-O bond activation of the corresponding Mn(III)-peroxo adduct. The peroxomanganese(III) intermediate, [Mn(III)(O2)(Me2EBC)](+), was prepared at low-temperature by the addition of KO2 to [Mn(II)(Cl)2(Me2EBC)] in CH2Cl2, and this complex was characterized by electronic absorption, electron paramagnetic resonance (EPR), and Mn K-edge X-ray absorption (XAS) spectroscopies. The electronic structure of the [Mn(III)(O2)(Me2EBC)](+) intermediate was examined by density functional theory (DFT) and time-dependent (TD) DFT calculations. Deta...Continue Reading

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Citations

Nov 18, 2016·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Adam T Fiedler, Anne A Fischer
Sep 6, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Melissa C DenlerTimothy A Jackson
Apr 4, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Chien-Ming LeeWonwoo Nam
Oct 21, 2017·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Derek B RiceTimothy A Jackson

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