A mononuclear nonheme iron(iv)-oxo complex which is more reactive than cytochrome P450 model compound I

• DOI: 10.1039/c1sc00062d
• Publication Date: 2011-04-01T11:06:13Z
• Authors: Mi Sook Seo; Nam Hee Kim; Kyung-Bin Cho; Jeong Eun So; Seon Kyung Park; Martin Clémancey; Ricardo Garcia-Se...; Jean-Marc Latour; Sason Shaik; Wonwoo Nam
• Keywords: [CHIM.COOR]Chemical Sciences/Coordination chemistry; 01 natural sciences; 0104 chemical sciences

A highly reactive mononuclear nonheme iron(IV)-oxo complex with a low-spin (S = 1) triplet ground state in both C–H bond activation and oxo transfer reactions is reported; this nonheme iron(IV)-oxo complex is more reactive than an iron(IV)-oxo porphyrin π-cation radical (i.e., a model of cytochrome P450 compound I) and is the most reactive species in kinetic studies among nonheme iron(IV)-oxo complexes reported so far. DFT calculations support the experimental results with extremely low activation barriers in the C–H bond activation of cyclohexane and 1,4-cyclohexadiene. The DFT calculations reveal that the S = 1 state is set up to easily lead to the highly reactive S = 2 high-spin iron(IV)-oxo species.