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学科主题: 物理化学
题名: Theoretical study on the mechanism for NH3BH3 reduction of ketones and imines
作者: Wang, Xu1, 2;  Yao, Wei1;  Zhou, Danhong2;  Fan, Hongjun1
通讯作者: 周丹红 ;  樊红军
关键词: reaction mechanism ;  ammonia borane ;  hydrogenation ;  ketone ;  amine
刊名: MOLECULAR PHYSICS
发表日期: 2013-10-31
DOI: 10.1080/00268976.2013.766366
卷: 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
类目[WOS]: Physics, Atomic, Molecular & Chemical
资助者: 1,1
研究领域[WOS]: Physics
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).
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
语种: 英语
原文出处: 查看原文
WOS记录号: WOS:000328101900003
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/119135
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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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

Recommended Citation:
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.
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