title: DFT study of the reaction of a two-coordinate iron(II) dialkyl complex with molecular oxygen.
abstract: DFT studies are reported of a monomeric iron dialkyl for which oxygen atom insertion into metal-methyl bonds occurs with O2: FeMe2 + O2 → Fe(OMe)2. Computation of the reaction coordinate implicates the intermediacy of Fe(III)-peroxo, Fe(VI)-dioxo, and Fe(IV)-oxo intermediates, connected by O2 oxidative addition and two methyl migration steps. Analysis of the reaction of O2 with d(6)-Fe(Me)2 indicates that oxy-insertion for this iron complex occurs with lower free energy barriers than competing homolytic/radical pathways, exploiting "spin-flip" processes via minimum energy crossing points (MECPs).
authors.affiliation: Center for Research on Complex Networks (CRCN), Department of Physics, Texas Southern University , Houston, Texas 77004, United States.
authors.forename: Bruce M
authors.initials: BM
authors.lastname: Prince
authors.forename: Thomas R
authors.initials: TR
authors.lastname: Cundari
authors.forename: C J
authors.initials: CJ
authors.lastname: Tymczak