title: How axial ligands control the reactivity of high-valent iron(IV)-oxo porphyrin pi-cation radicals in alkane hydroxylation: a computational study.
abstract: The push effect of anionic axial ligands of high-valent iron(IV)-oxo porphyrin pi-cation radicals, (Porp)(+.)Fe(IV)(O)(X) (X=OH(-), AcO(-), Cl(-), and CF(3)SO(3)(-)), in alkane hydroxylation is investigated by B3LYP DFT calculations. The electron-donating ability of anionic axial ligands influences the activation energy for the alkane hydroxylation by the iron(IV)-oxo intermediates and the Fe-O bond distance of the iron-oxo species in transition state.
authors.affiliation: Institute for Materials Chemistry and Engineering, Kyushu University, Fukuoka 812-8581, Japan.
authors.forename: Takashi
authors.initials: T
authors.lastname: Kamachi
authors.forename: Tomohisa
authors.initials: T
authors.lastname: Kouno
authors.forename: Wonwoo
authors.initials: W
authors.lastname: Nam
authors.forename: Kazunari
authors.initials: K
authors.lastname: Yoshizawa
mesh_terms: D000473:Alkanes / Q000737:chemistry*; D003198:Computer Simulation; D006900:Hydroxylation; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D010100:Oxygen / Q000737:chemistry; D011166:Porphyrins / Q000737:chemistry*
chemical_list: D000473:Alkanes; D008024:Ligands; D011166:Porphyrins; C028565:porphyrin pi cation radical; C066317:ferryl iron; D007501:Iron; D010100:Oxygen