Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 55, Issue 11, Pages 3709-3713Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201600287
Keywords
bioinorganic chemistry; electron transfer; iron(IV)-imido complexes; mechanisms; N-demethylation
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Funding
- NRF of Korea through CRI [NRF-2012R1A3A2048842]
- NRF of Korea through GRL [NRF-2010-00353]
- JST, Japan
- JSPS from MEXT [26620154, 26288037]
- Grants-in-Aid for Scientific Research [26288037, 16K13964, 26620154] Funding Source: KAKEN
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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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