title: Enhanced Electron Transfer Reactivity of a Nonheme Iron(IV)-Imido Complex as Compared to the Iron(IV)-Oxo Analogue.
abstract: Reactions of N,N-dimethylaniline (DMA) with nonheme iron(IV)-oxo and iron(IV)-tosylimido complexes occur via different mechanisms, such as an N-demethylation of DMA by a nonheme iron(IV)-oxo complex or an electron transfer dimerization of DMA by a nonheme iron(IV)-tosylimido complex. The change in the reaction mechanism results from the greatly enhanced electron transfer reactivity of the iron(IV)-tosylimido complex, such as the much more positive one-electron reduction potential and the smaller reorganization energy during electron transfer, as compared to the electron transfer properties of the corresponding iron(IV)-oxo complex.
authors.affiliation: Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 03760, Korea.
authors.forename: Anil Kumar
authors.initials: AK
authors.lastname: Vardhaman
authors.affiliation: Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 03760, Korea.
authors.forename: Yong-Min
authors.initials: YM
authors.lastname: Lee
authors.affiliation: Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 03760, Korea.
authors.forename: Jieun
authors.initials: J
authors.lastname: Jung
authors.affiliation: Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 03760, Korea.|Faculty of Science and Engineering, ALCA, SENTAN, Japan Science and Technology Agency (JST), Meijo University, Nagoya, Aichi, 468-0073, Japan.|Department of Material and Life Science, Graduate School of Engineering, ALCA, SENTAN, Japan Science and Technology Agency (JST), Osaka University, Suita, Osaka, 565-0871, Japan.
authors.forename: Kei
authors.initials: K
authors.lastname: Ohkubo
authors.affiliation: Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 03760, Korea. wwnam@ewha.ac.kr.
authors.forename: Wonwoo
authors.initials: W
authors.lastname: Nam
authors.affiliation: Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 03760, Korea.|Faculty of Science and Engineering, ALCA, SENTAN, Japan Science and Technology Agency (JST), Meijo University, Nagoya, Aichi, 468-0073, Japan.
authors.forename: Shunichi
authors.initials: S
authors.lastname: Fukuzumi
keywords: N-demethylation; bioinorganic chemistry; electron transfer; iron(IV)-imido complexes; mechanisms