title: Mechanistic insights into iron catalyzed dehydrogenation of formic acid: β-hydride elimination vs. direct hydride transfer.
abstract: Density functional theory calculations reveal a complete reaction mechanism with detailed energy profiles and transition state structures for the dehydrogenation of formic acid catalyzed by an iron complex, [P(CH2CH2PPh2)3FeH](+). In the cationic reaction pathway, a β-hydride elimination process is confirmed to be the rate-determining step in this catalytic reaction. A potential reaction pathway starting with a direct hydride transfer from HCOO(-) to Fe is found to be possible, but slightly less favorable than the catalytic cycle with a β-hydride elimination step.
authors.affiliation: State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China. xyang@iccas.ac.cn
authors.forename: Xinzheng
authors.initials: X
authors.lastname: Yang
mesh_terms: D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry*; D005290:Ferric Compounds / Q000737:chemistry*; D005561:Formates / Q000737:chemistry*; D006865:Hydrogenation; D015394:Molecular Structure; D011789:Quantum Theory
chemical_list: D056831:Coordination Complexes; D005290:Ferric Compounds; D005561:Formates; C030544:formic acid