Unexpected Direct Hydride Transfer Mechanism for the Hydrogenation of Ethyl Acetate to Ethanol Catalyzed by SNS Pincer Ruthenium Complexes

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	Unexpected Direct Hydride Transfer Mechanism for the Hydrogenation of Ethyl Acetate to Ethanol Catalyzed by SNS Pincer Ruthenium Complexes
	Chen, Xiangyang 1,2; Jing, Yuanyuan 1; Yang, Xinzheng 1
刊名	CHEMISTRY-A EUROPEAN JOURNAL
	2016-02-05
卷号	22 期号:6 页码:1950-1957
关键词	density functional calculations hydrogenation pincer ligands reaction mechanisms ruthenium
英文摘要	The hydrogenation of ethyl acetate to ethanol catalyzed by SNS pincer ruthenium complexes was computationally investigated by using DFT. Different from a previously proposed mechanism with fac-[(SNS)Ru(PPh3)(H)(2)] (5) as the catalyst, an unexpected direct hydride transfer mechanism with a mer-SNS ruthenium complex as the catalyst, and two cascade catalytic cycles for hydrogenations of ethyl acetate to aldehyde and aldehyde to ethanol, is proposed base on our calculations. The new mechanism features ethanol-assisted proton transfer for H-2 cleavage, direct hydride transfer from ruthenium to the carbonyl carbon, and C-OEt bond cleavage. Calculation results indicate that the rate-determining step in the whole catalytic reaction is the transfer of a hydride from ruthenium to the carbonyl carbon of ethyl acetate, with a total free energy barrier of only 26.9kcalmol(-1), which is consistent with experimental observations and significantly lower than the relative free energy of an intermediate in a previously postulated mechanism with 5 as the catalyst.
收录类别	SCI
语种	英语
公开日期	2016-05-03
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/30104]
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, Beijing Natl Lab Mol Sci, State Key Lab Struct Chem Unstable & Stable Speci, 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. Unexpected Direct Hydride Transfer Mechanism for the Hydrogenation of Ethyl Acetate to Ethanol Catalyzed by SNS Pincer Ruthenium Complexes[J]. CHEMISTRY-A EUROPEAN JOURNAL,2016,22(6):1950-1957.
APA	Chen, Xiangyang,Jing, Yuanyuan,&Yang, Xinzheng.(2016).Unexpected Direct Hydride Transfer Mechanism for the Hydrogenation of Ethyl Acetate to Ethanol Catalyzed by SNS Pincer Ruthenium Complexes.CHEMISTRY-A EUROPEAN JOURNAL,22(6),1950-1957.
MLA	Chen, Xiangyang,et al."Unexpected Direct Hydride Transfer Mechanism for the Hydrogenation of Ethyl Acetate to Ethanol Catalyzed by SNS Pincer Ruthenium Complexes".CHEMISTRY-A EUROPEAN JOURNAL 22.6(2016):1950-1957.