Enhanced Electron Transfer Reactivity of a Nonheme Iron(IV)–Imido Complex as Compared to the Iron(IV)‐Oxo Analogue |
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| Authors: | Dr. Anil Kumar Vardhaman Dr. Yong‐Min Lee Dr. Jieun Jung Dr. Kei Ohkubo Prof. Dr. Wonwoo Nam Prof. Dr. Shunichi Fukuzumi |
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| Affiliation: | 1. Department of Chemistry and Nano Science, Ewha Womans University, Seoul, Korea;2. Faculty of Science and Engineering, ALCA, SENTAN, Japan Science and Technology Agency (JST), Meijo University, Nagoya, Aichi, Japan;3. Department of Material and Life Science, Graduate School of Engineering, ALCA, SENTAN, Japan Science and Technology Agency (JST), Osaka University, Suita, Osaka, Japan |
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| 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. |
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| Keywords: | bioinorganic chemistry electron transfer iron(IV)-imido complexes mechanisms N-demethylation |
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