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学科主题物理化学
Theoretical study on the mechanism for NH3BH3 reduction of ketones and imines
Wang, Xu1,2; Yao, Wei1; Zhou, Danhong2; Fan, Hongjun1; Zhou DH(周丹红); Fan HJ(樊红军)
关键词Reaction Mechanism Ammonia Borane Hydrogenation Ketone Amine
刊名MOLECULAR PHYSICS
2013-10-31
DOI10.1080/00268976.2013.766366
111期:20页:3014-3024
收录类别SCI
合作性质
文章类型Article
部门归属11
项目归属1102
产权排名待补充
WOS标题词Science & Technology ; Physical Sciences
资助者1,1 ; 1,1 ; 1,1 ; 1,1
类目[WOS]Physics, Atomic, Molecular & Chemical
研究领域[WOS]Physics
关键词[WOS]AMMONIA-BORANE DEHYDROGENATION ; CHEMICAL HYDROGEN STORAGE ; N-H COMPOUNDS ; CATALYZED DEHYDROGENATION ; THERMAL-DECOMPOSITION ; CORRELATION ENERGIES ; DENSITY FUNCTIONALS ; BASIS-SETS ; RELEASE ; BORON
英文摘要In spite of a potential hydrogen storage material, ammonia borane (AB) was recently found to be a good hydrogenation reagent. It can reduce certain ketones to alcohols or borate esters, and imines to amines. The mechanisms of these reactions are not fully understood yet, and have been systematically studied using high-level CCSD(T) calculations in this work. We have validated theoretically that the forming of alcohols and amines undergoes concerted double-hydrogen transfer (DHT) mechanism. Furthermore, we predicted that the DHT process is facile for more general ketones and imines. For the borate ester formation, we found a pretty high barrier for the experimentally derived stepwise mechanism. Alternatively, we propose that the reaction starts with the DHT process to form alcohol and NH2BH2, followed by alcoholysis of NH2BH2 to form the first B-O bond. This mechanism is in good agreement with the current experimental facts, and also explains why ketone reduction affords different products at different conditions. For these reaction systems, the performances of M06-2x and MP2 (underestimate the barrier by 5-7 kcal/mol, but with right trends) are better than B3LYP and BLYP methods (underestimate the barrier by 0-5 kcal/mol).
语种英语
资助者1,1 ; 1,1 ; 1,1 ; 1,1
原文出处查看原文
WOS记录号WOS:000328101900003
引用统计
被引频次:2[WOS]   [WOS记录]     [WOS相关记录]
文献类型期刊论文
条目标识符http://cas-ir.dicp.ac.cn/handle/321008/119135
专题中国科学院大连化学物理研究所
通讯作者Zhou DH(周丹红); Fan HJ(樊红军)
作者单位1.Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China
2.Liaoning Normal Univ, Dalian 116029, Peoples R China
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GB/T 7714
Wang, Xu,Yao, Wei,Zhou, Danhong,et al. Theoretical study on the mechanism for NH3BH3 reduction of ketones and imines[J]. MOLECULAR PHYSICS,2013,111(20):3014-3024.
APA Wang, Xu,Yao, Wei,Zhou, Danhong,Fan, Hongjun,周丹红,&樊红军.(2013).Theoretical study on the mechanism for NH3BH3 reduction of ketones and imines.MOLECULAR PHYSICS,111(20),3014-3024.
MLA Wang, Xu,et al."Theoretical study on the mechanism for NH3BH3 reduction of ketones and imines".MOLECULAR PHYSICS 111.20(2013):3014-3024.
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