title: Bioinspired Design and Computational Prediction of Iron Complexes with Pendant Amines for the Production of Methanol from CO2 and H2.
abstract: Inspired by the active site structure of [FeFe]-hydrogenase, we built a series of iron dicarbonyl diphosphine complexes with pendant amines and predicted their potentials to catalyze the hydrogenation of CO2 to methanol using density functional theory. Among the proposed iron complexes, [(P(tBu)2N(tBu)2H)FeH(CO)2(COOH)](+) (5COOH) is the most active one with a total free energy barrier of 23.7 kcal/mol. Such a low barrier indicates that 5COOH is a very promising low-cost catalyst for high-efficiency conversion of CO2 and H2 to methanol under mild conditions. For comparison, we also examined Bullock's Cp iron diphosphine complex with pendant amines, [(P(tBu)2N(tBu)2H)FeHCp(C5F4N)](+) (5Cp-C5F4N), as a catalyst for hydrogenation of CO2 to methanol and obtained a total free energy barrier of 27.6 kcal/mol, which indicates that 5Cp-C5F4N could also catalyze the conversion of CO2 and H2 to methanol but has a much lower efficiency than our newly designed iron complexes.
authors.affiliation: Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, People's Repubic of China.|University of Chinese Academy of Sciences , Beijing 100049, People's Repubic of China.
authors.forename: Xiangyang
authors.initials: X
authors.lastname: Chen
authors.affiliation: Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, People's Repubic of China.
authors.forename: Xinzheng
authors.initials: X
authors.lastname: Yang
mesh_terms: D000588:Amines / Q000737:chemistry; D040761:Biomimetic Materials / Q000737:chemistry*; D002245:Carbon Dioxide / Q000737:chemistry*; D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D058085:Iron Compounds / Q000737:chemistry*; D000432:Methanol / Q000138:chemical synthesis*; D008956:Models, Chemical
chemical_list: D000588:Amines; D056831:Coordination Complexes; D058085:Iron Compounds; D002245:Carbon Dioxide; D006859:Hydrogen; D000432:Methanol