title: A density functional theory study of the reaction of the biomimetic iron(II) complex of a tetradentate bispidine ligand with H2O2.
abstract: Three pathways for the reaction of bispidine-iron(II) complexes (where bispidine is a rigid tetradentate amine/pyridine ligand) with H2O2 have been studied by DFT calculations. For all oxidation states the high-spin and low-spin (intermediate-spin) forms have been optimized, and the computed data have been compared with the readily available experimental results. It is concluded that there is a direct conversion of the bispidine-iron(II)-hydrogen peroxide complex to the corresponding iron(IV)-dihydroxo compound, which is a novel possible oxidant for the dihydroxylation of olefins.
authors.affiliation: Universität Heidelberg, Anorganisch-Chemisches Institut, Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany. peter.comba@aci.uni-heidelberg.de
authors.forename: Peter
authors.initials: P
authors.lastname: Comba
authors.forename: Gopalan
authors.initials: G
authors.lastname: Rajaraman
authors.forename: Heidi
authors.initials: H
authors.lastname: Rohwer
mesh_terms: D000475:Alkenes / Q000737:chemistry; D032701:Biomimetics; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000737:chemistry*; D019295:Computational Biology; D006861:Hydrogen Peroxide / Q000737:chemistry*; D058085:Iron Compounds / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D010084:Oxidation-Reduction
chemical_list: D000475:Alkenes; D019086:Bridged Bicyclo Compounds, Heterocyclic; D058085:Iron Compounds; D008024:Ligands; C495809:bispidine; D006861:Hydrogen Peroxide