Density functional theory study on the mechanism and thermochemistry of olefins addition to nickel dithiolenes

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	Density functional theory study on the mechanism and thermochemistry of olefins addition to nickel dithiolenes
	Sun, Li-Li 1,2; Zhang, Sheng-Fei 1,2; Han Qing-Zhen 1; Zhao Yue-Hong 1; Hao, Wen 1
刊名	MOLECULAR SIMULATION
	2011
卷号	37 期号:10 页码:813-823
关键词	nickel dithiolenes olefins reaction mechanism thermochemical property
ISSN号	0892-7022
通讯作者	Sun, LL
英文摘要	We investigated the reaction mechanism and thermochemical property of conjugated dienes or mono-olefins with nickel dithiolenes (Ni(S2C2R2)(2)) using density functional theory. The reactions between conjugated dienes and nickel dithiolenes are concerted reactions. The thermochemical property study shows that the introduction of electron-withdrawing groups (-CF3 or -CN) to nickel dithiolene (Ni(S2C2H2)(2)) not only significantly lowers the activation energy barrier but also strongly stabilises the products. The introduction of electron-donating group (-CH3) to butadiene has the same effect. So, we conclude that the reactions between nickel dithiolenes and conjugated dienes are electrophilic cycloaddition. Mono-olefins can add to nickel dithiolenes through interligand pathway, which is a two-step process or through intraligand pathway, which is a one-step process. The thermochemical property study shows that the activation enthalpy for the reaction of butadiene with Ni(S2C2(CF3)(2))(2) is much lower than those of C4 mono-olefins with Ni(S2C2(CF3)(2))(2) for both interligand addition and intraligand addition. The Gibbs free energy for the reaction of butadiene with Ni(S2C2(CF3)(2))(2) is also more favourable than those of C4 mono-olefins with Ni(S2C2(CF3)(2))(2). It is the very preferential pathway for Ni(S2C2(CF3)(2))(2) to bind butadiene than C4 mono-olefins.
WOS标题词	Science & Technology ; Physical Sciences
类目[WOS]	Chemistry, Physical ; Physics, Atomic, Molecular & Chemical
研究领域[WOS]	Chemistry ; Physics
关键词[WOS]	EFFECTIVE CORE POTENTIALS ; SET MODEL CHEMISTRY ; MOLECULAR CALCULATIONS ; ADSORPTIVE SEPARATION ; TOTAL ENERGIES ; LIGHT OLEFINS ; COMPLEXES ; ATOMS ; CYCLOADDITION ; POLARIZATION
收录类别	SCI
语种	英语
WOS记录号	WOS:000294152700001
公开日期	2013-10-31
内容类型	期刊论文
版本	出版稿
源URL	[http://ir.ipe.ac.cn/handle/122111/4642]
专题	过程工程研究所_多相复杂系统国家重点实验室
作者单位	1.Chinese Acad Sci, Inst Proc Engn, State Key Lab Multiphase Complex Syst, Beijing 100190, Peoples R China 2.Chinese Acad Sci, Grad Univ, Beijing 100049, Peoples R China
推荐引用方式 GB/T 7714	Sun, Li-Li,Zhang, Sheng-Fei,Han Qing-Zhen,et al. Density functional theory study on the mechanism and thermochemistry of olefins addition to nickel dithiolenes[J]. MOLECULAR SIMULATION,2011,37(10):813-823.
APA	Sun, Li-Li,Zhang, Sheng-Fei,Han Qing-Zhen,Zhao Yue-Hong,&Hao, Wen.(2011).Density functional theory study on the mechanism and thermochemistry of olefins addition to nickel dithiolenes.MOLECULAR SIMULATION,37(10),813-823.
MLA	Sun, Li-Li,et al."Density functional theory study on the mechanism and thermochemistry of olefins addition to nickel dithiolenes".MOLECULAR SIMULATION 37.10(2011):813-823.