Trivalent Uranium Complex As a Catalyst to Promote the Functionalization of Carbon Dioxide and Carbon Disulfide: A Computational Mechanistic Study

	Trivalent Uranium Complex As a Catalyst to Promote the Functionalization of Carbon Dioxide and Carbon Disulfide: A Computational Mechanistic Study
	Ding, WJ; Fang, WH; Chai ZF(柴之芳); 王东琪;Chai, ZF; Wang, DQ
刊名	JOURNAL OF CHEMICAL THEORY AND COMPUTATION
	2012
卷号	8 期号:10 页码:3605-3617
英文摘要	We report our recent DFT mechanistic study on the functionalization of CO2 and CS2 promoted by a trivalent uranium complex (Tp*)(2)UCH2Ph. In the calculations, the uranium atom is described by a quasi-relativistic 5f-in-core ECP basis set (LPP) developed for the trivalent uranium cation, which was qualified by the calculations with a quasi-relativistic small core ECP basis set (SPP) for uranium. According to our calculations, the functionalization proceeds in a stepwise manner, and the CO2 or CS2 does not interact with the central uranium atom to form a stable complex prior to the reaction due to the steric hindrance from the bulky ligands but directly cleaves the U-C (benzyl) bond by forming a C-C covalent bond. The released coordination site of uranium is concomitantly occupied by one chalcogen atom of the incoming molecule and gives an intermediate with the uranium atom interacting with the functionalized CO2 or CS2 in an eta(1) fasion. This step is followed by a reorientation of the (dithio)carboxylate side chain of the newly formed PhCH2CE2- (E = O, S) ligand to give the corresponding product. Energetically, the first step is characterized as the rate-determining step with a barrier of 9.5 (CO2) or 25.0 (CS2) kcal/mol, and during the reaction, the chalcogen atoms are reduced, while the methylene of the benzyl group is oxidized. Comparison of the results from SPP and LPP calculations indicates that our calculations qualify the use of an LPP treatment of the uranium atom toward a reasonable description of the model systems in the present study.
学科主题	Chemistry; Physics
收录类别	SCI
WOS记录号	WOS:000309505600018
公开日期	2016-05-03
内容类型	期刊论文
源URL	[http://ir.ihep.ac.cn/handle/311005/224236]
专题	高能物理研究所_院士
推荐引用方式 GB/T 7714	Ding, WJ,Fang, WH,Chai ZF,et al. Trivalent Uranium Complex As a Catalyst to Promote the Functionalization of Carbon Dioxide and Carbon Disulfide: A Computational Mechanistic Study[J]. JOURNAL OF CHEMICAL THEORY AND COMPUTATION,2012,8(10):3605-3617.
APA	Ding, WJ,Fang, WH,柴之芳,王东琪；Chai, ZF,&Wang, DQ.(2012).Trivalent Uranium Complex As a Catalyst to Promote the Functionalization of Carbon Dioxide and Carbon Disulfide: A Computational Mechanistic Study.JOURNAL OF CHEMICAL THEORY AND COMPUTATION,8(10),3605-3617.
MLA	Ding, WJ,et al."Trivalent Uranium Complex As a Catalyst to Promote the Functionalization of Carbon Dioxide and Carbon Disulfide: A Computational Mechanistic Study".JOURNAL OF CHEMICAL THEORY AND COMPUTATION 8.10(2012):3605-3617.