DFT study of the reaction of a two-coordinate iron(II) dialkyl complex with molecular oxygen

Bruce M Prince; Thomas R Cundari; C J Tymczak

doi:10.1021/jp5082438

DFT study of the reaction of a two-coordinate iron(II) dialkyl complex with molecular oxygen

J Phys Chem A. 2014 Nov 20;118(46):11056-61. doi: 10.1021/jp5082438. Epub 2014 Nov 11.

Authors

Bruce M Prince¹, Thomas R Cundari, C J Tymczak

Affiliation

¹ Center for Research on Complex Networks (CRCN), Department of Physics, Texas Southern University , Houston, Texas 77004, United States.

PMID: 25355170
DOI: 10.1021/jp5082438

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).