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