title: Oxidation of cyclohexane by a high-valent iron bispidine complex: a combined experimental and computational mechanistic study.
abstract: Experimental data suggest that there are various competing pathways for the catalytic and stoichiometric oxygenation of cyclohexane, assisted by iron-bispidine complexes and using various oxidants (H(2)O(2), O(2), PhIO). Density functional theory calculations indicate that both Fe(IV)=O and Fe(V)=O species are accessible and efficiently transfer their oxygen atoms to cyclohexane. The reactivities of the two isomers each and the two possible spin states for the Fe(IV)=O and Fe(V)=O species are sufficiently different to allow an interpretation of the experimental data.
authors.affiliation: Universität Heidelberg, Anorganisch-Chemisches Institut, INF 270, D-69120 Heidelberg, Germany. peter.comba@aci.uni-heidelberg.de
authors.forename: Peter
authors.initials: P
authors.lastname: Comba
authors.forename: Martin
authors.initials: M
authors.lastname: Maurer
authors.forename: Prabha
authors.initials: P
authors.lastname: Vadivelu
mesh_terms: D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000737:chemistry*; D003510:Cyclohexanes / Q000737:chemistry* / Q000378:metabolism; D006861:Hydrogen Peroxide / Q000737:chemistry; D006900:Hydroxylation; D007501:Iron / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D016877:Oxidants / Q000737:chemistry; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry
chemical_list: D019086:Bridged Bicyclo Compounds, Heterocyclic; D003510:Cyclohexanes; D016877:Oxidants; C495809:bispidine; C506365:Cyclohexane; D006861:Hydrogen Peroxide; D007501:Iron; D010100:Oxygen