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Computational Design of Iron Diphosphine Complexes with Pendant Amines for Hydrogenation of CO 2 to Methanol: A Mimic of [NiFe] Hydrogenase
Author(s) -
Chen Xiangyang,
Jing Yuanyuan,
Yang Xinzheng
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600764
Subject(s) - chemistry , formic acid , hydride , catalysis , methanol , ligand (biochemistry) , medicinal chemistry , transfer hydrogenation , hydrogenase , aqueous solution , bond cleavage , amine gas treating , density functional theory , photochemistry , inorganic chemistry , polymer chemistry , hydrogen , organic chemistry , computational chemistry , ruthenium , biochemistry , receptor
Inspired by the active‐site structure of the [NiFe] hydrogenase, we have computationally designed the iron complex [P t Bu 2 N t Bu 2 )Fe(CN) 2 CO] by using an experimentally ready‐made diphosphine ligand with pendant amines for the hydrogenation of CO 2 to methanol. Density functional theory calculations indicate that the rate‐determining step in the whole catalytic reaction is the direct hydride transfer from the Fe center to the carbon atom in the formic acid with a total free energy barrier of 28.4 kcal mol −1 in aqueous solution. Such a barrier indicates that the designed iron complex is a promising low‐cost catalyst for the formation of methanol from CO 2 and H 2 under mild conditions. The key role of the diphosphine ligand with pendent amine groups in the reaction is the assistance of the cleavage of H 2 by forming a Fe−H δ− ⋅⋅⋅H δ+ −N dihydrogen bond in a fashion of frustrated Lewis pairs.