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Mechanistic Investigation of Oxygen Rebound in a Mononuclear Nonheme Iron Complex.

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.

SUBMITTER: Pangia TM 

PROVIDER: S-EPMC7909310 | biostudies-literature | 2019 Aug

REPOSITORIES: biostudies-literature

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Mechanistic Investigation of Oxygen Rebound in a Mononuclear Nonheme Iron Complex.

Pangia Thomas M TM   Yadav Vishal V   Gérard Emilie F EF   Lin Yen-Ting YT   de Visser Sam P SP   Jameson Guy N L GNL   Goldberg David P DP  

Inorganic chemistry 20190717 15

An iron(III) methoxide complex reacts with <i>para</i>-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 invo  ...[more]