title: Nonheme iron-oxo and -superoxo reactivities: O2 binding and spin inversion probability matter.
abstract: DFT calculated barriers for C-H activation of 1,4-cyclohexadiene by nonheme iron(IV)-oxo and iron(III)-superoxo species show that the experimental trends can be explained if the spin inversion probability of the TMC iron(IV)-oxo is assumed to be poor. Also, the TMC iron(III)-superoxo reaction proceeds with an endothermic O(2)-binding energy followed by an intrinsically reactive quintet state.
authors.affiliation: Dept of Bioinspired Chemistry, Ewha Womans University, Seoul 120-750, Korea.
authors.forename: Kyung-Bin
authors.initials: KB
authors.lastname: Cho
authors.forename: Hui
authors.initials: H
authors.lastname: Chen
authors.forename: Deepa
authors.initials: D
authors.lastname: Janardanan
authors.forename: Sam P
authors.initials: SP
authors.lastname: de Visser
authors.forename: Sason
authors.initials: S
authors.lastname: Shaik
authors.forename: Wonwoo
authors.initials: W
authors.lastname: Nam
mesh_terms: D053138:Cyclohexenes / Q000737:chemistry*; D058085:Iron Compounds / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D010100:Oxygen / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D053138:Cyclohexenes; D058085:Iron Compounds; D008024:Ligands; C048401:1,4-cyclohexadiene; D010100:Oxygen