Theoretical study on the mechanism for NH3BH3 reduction of ketones and imines

	Theoretical study on the mechanism for NH3BH3 reduction of ketones and imines
	Wang, Xu 1,2; Yao, Wei 1; Zhou, Danhong 2; Fan, Hongjun 1
刊名	molecular physics
	2013-10-31
卷号	111 期号:20 页码:3014-3024
关键词	reaction mechanism ammonia borane hydrogenation ketone amine
通讯作者	周丹红 ; 樊红军
产权排序	待补充
合作状况	英
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).
学科主题	物理化学
WOS标题词	science & technology ; physical sciences
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
收录类别	SCI
资助信息	1，1
原文出处	3024
语种	英语
WOS记录号	WOS:000328101900003
公开日期	2014-09-11
内容类型	期刊论文
源URL	[http://159.226.238.44/handle/321008/119135]
专题	大连化学物理研究所_中国科学院大连化学物理研究所
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
推荐引用方式 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.(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.