DICP OpenIR
Subject Area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)
KeywordReaction Mechanism Ammonia Borane Hydrogenation Ketone Amine
Source PublicationMOLECULAR PHYSICS
2013-10-31
DOI10.1080/00268976.2013.766366
Volume111Issue:20Pages:3014-3024
Indexed BySCI
Cooperation Status
SubtypeArticle
Department11
Funding Project1102
Contribution Rank待补充
WOS HeadingsScience & Technology ; Physical Sciences
Funding Organization1,1 ; 1,1 ; 1,1 ; 1,1
WOS SubjectPhysics, Atomic, Molecular & Chemical
WOS Research AreaPhysics
WOS KeywordAMMONIA-BORANE DEHYDROGENATION ; CHEMICAL HYDROGEN STORAGE ; N-H COMPOUNDS ; CATALYZED DEHYDROGENATION ; THERMAL-DECOMPOSITION ; CORRELATION ENERGIES ; DENSITY FUNCTIONALS ; BASIS-SETS ; RELEASE ; BORON
AbstractIn 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).
Language英语
Funding Organization1,1 ; 1,1 ; 1,1 ; 1,1
URL查看原文
WOS IDWOS:000328101900003
Citation statistics
Cited Times:2[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/119135
Collection中国科学院大连化学物理研究所
Corresponding AuthorZhou DH(周丹红); Fan HJ(樊红军)
Affiliation1.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
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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