The role of substrate in unmasking oxyl character in oxomanganese complexes: the key to selectivity?
The reaction profile for sulfide oxidation by formally Mn(V)=O species depends critically on the electronic structure of the isolated oxidant. In cases where the ground state has dominant oxyl radical character, the oxidation occurs in sequential one-electron steps, the first of which is barrierless. In contrast, if the oxyl radical character is 'masked' in the ground state by electron transfer from either the metal or the porphyrin co-ligand, the interaction between oxidant and substrate is ...Expand abstract
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