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.
Bibliographical noteFunding Information:
This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.), GRL (NRF-2010-00353 to W.N.) and ALCA and SENTAN projects from JST, Japan (to S.F.) and JSPS (26620154 and 26288037) from MEXT (to K.O.).
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- bioinorganic chemistry
- electron transfer
- iron(IV)-imido complexes