Computational Design of Iron Diphosphine Complexes with Pendant Amines for Hydrogenation of CO2 to Methanol: A Mimic of [NiFe] Hydrogenase

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	Computational Design of Iron Diphosphine Complexes with Pendant Amines for Hydrogenation of CO2 to Methanol: A Mimic of [NiFe] Hydrogenase
	Chen, Xiangyang 1,2; Jing, Yuanyuan 1; Yang, Xinzheng 1
刊名	CHEMISTRY-A EUROPEAN JOURNAL
	2016-06-20
卷号	22 期号:26 页码:8897-8902
关键词	carbon dioxide density functional calculations hydrogenases hydrogenation methanol
英文摘要	Inspired by the active-site structure of the [NiFe] hydrogenase, we have computationally designed the iron complex [(P2N2tBu)-N-tBu)Fe(CN)(2)CO] by using an experimentally ready-made diphosphine ligand with pendant amines for the hydrogenation of CO2 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 CO2 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 delta-center dot center dot center dot H delta+-N dihydrogen bond in a fashion of frustrated Lewis pairs.
收录类别	SCI
语种	英语
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/35195]
专题	化学研究所_分子动态与稳态结构实验室
作者单位	1.Chinese Acad Sci, Inst Chem, State Key Lab Struct Chem Unstable & Stable Speci, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China 2.Univ Chinese Acad Sci, Beijing 100049, Peoples R China
推荐引用方式 GB/T 7714	Chen, Xiangyang,Jing, Yuanyuan,Yang, Xinzheng. Computational Design of Iron Diphosphine Complexes with Pendant Amines for Hydrogenation of CO2 to Methanol: A Mimic of [NiFe] Hydrogenase[J]. CHEMISTRY-A EUROPEAN JOURNAL,2016,22(26):8897-8902.
APA	Chen, Xiangyang,Jing, Yuanyuan,&Yang, Xinzheng.(2016).Computational Design of Iron Diphosphine Complexes with Pendant Amines for Hydrogenation of CO2 to Methanol: A Mimic of [NiFe] Hydrogenase.CHEMISTRY-A EUROPEAN JOURNAL,22(26),8897-8902.
MLA	Chen, Xiangyang,et al."Computational Design of Iron Diphosphine Complexes with Pendant Amines for Hydrogenation of CO2 to Methanol: A Mimic of [NiFe] Hydrogenase".CHEMISTRY-A EUROPEAN JOURNAL 22.26(2016):8897-8902.