A Mononuclear Nonheme Iron(IV)–Amido Complex Relevant for the Compound II Chemistry of Cytochrome P450

Xiaoyan Lu (1) , Xiao-Xi Li (1) , Mi Sook Seo (1) , Yong-Min Lee (1) , Martin Clémancey (2) , Pascale Maldivi (3, 4) , Jean-Marc Latour (2) , Ritimukta Sarangi (5) , Shunichi Fukuzumi (1) , Wonwoo Nam (1, 6)

1 Department of Chemistry and Nano Science
2 PMB - Physiochimie des Métaux
3 CAMPE - Conception d’Architectures Moléculaires et Processus Electroniques
4 DIESE - Département Interfaces pour l'énergie, la Santé et l'Environnement
5 SSRL SLAC - Stanford Synchrotron Radiation Lightsource
6 Lanzhou Institute of Chemical Physics (LICP)

A mononuclear nonheme iron(IV)–amido complex bearing a tetraamido macrocyclic ligand, [(TAML)FeIV(NHTs)]− (1), was synthesized via a hydrogen atom (H atom) abstraction reaction of an iron(V)–imido complex, [(TAML)FeV(NTs)]− (2), and fully characterized using various spectroscopies. We then investigated (1) the pKa of 1, (2) the reaction of 1 with a carbon-centered radical, and (3) the H atom abstraction reaction of 1. To the best of our knowledge, the present study reports for the first time the synthesis and chemical properties/reactions of a high-valent iron(IV)–amido complex.

Domaines: Chimie théorique et/ou physique

Xiaoyan Lu, Xiao-Xi Li, Mi Sook Seo, Yong-Min Lee, Martin Clémancey, et al.. A Mononuclear Nonheme Iron(IV)–Amido Complex Relevant for the Compound II Chemistry of Cytochrome P450. Journal of the American Chemical Society, 2019, 141 (1), pp.80-83. ⟨10.1021/jacs.8b11045⟩. ⟨hal-02017334⟩