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Mechanistic Investigation of Oxygen Rebound in a Mononuclear Nonheme Iron Complex
Thomas M Pangia1, Vishal Yadav1, Emilie F Gérard2
1Department of Chemistry , The Johns Hopkins University , 3400 North Charles Street , Baltimore , Maryland 21218 , United States.
Abstract:
An iron(III) methoxide complex reacts with para-substituted triarylmethyl radicals to give iron(II) and methoxyether products. Second-order rate constants for the radical derivatives were obtained. Hammett and Marcus plots suggest the radical transfer reactions proceed via a concerted process. Calculations support the concerted nature of these reactions involving a single transition state with no initial charge transfer. These findings have implications for the radical "rebound" step invoked in nonheme iron oxygenases, halogenases, and related synthetic catalysts.
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