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	Quantum chemical study on influence of substituents and solvents in reaction complexing ethylene with nickel dithiolene
	Han, Qing-Zhen1,2; Zhao, Yue-Hong1; Wen, Hao1
刊名	MOLECULAR SIMULATION
	2008
卷号	34期号:6页码:631-636
关键词	substituent effects solvent effects activation energy rate constant
ISSN号	0892-7022
其他题名	Mol. Simul.
中文摘要	The influences induced by various terminal substituents and solvents on the reaction mechanism and chemical dynamics of complexing ethylene with Ni dithiolene are theoretically studied by using B3LYP method and Onsager model. It is shown that the reaction should be a two-step process, and the first step is the rate-determining step. We find that the rate constant of the rate-determining step becomes small when the electron-donating ability of the substituents is increased, while it becomes large when the electron-withdrawing ability of the substituents is increased. Subsequently, we consider the solvent effects on the reaction adding ethylene to the simplified hydrogen-substituted nickel dithiolene. It is found that the solvents will make slight changes to the geometries of the reactants, transition states, intermediates and products. However, the corresponding molecular dipole moments become large with the increase of the solvent polarity, which is beneficial to accelerate the reaction. Moreover, we show that, as the solvent polarity becomes large, the activation energies of the reaction decrease exponentially, while the reaction rate constants increase exponentially. These results demonstrate that in polar solvents, the reaction complexing ethylene with Ni dithiolene may become easier and faster to occur, and the product rate is improved. We believe that this research can be seen as a reference for complex and solvent selection in olefin separation process.
英文摘要	The influences induced by various terminal substituents and solvents on the reaction mechanism and chemical dynamics of complexing ethylene with Ni dithiolene are theoretically studied by using B3LYP method and Onsager model. It is shown that the reaction should be a two-step process, and the first step is the rate-determining step. We find that the rate constant of the rate-determining step becomes small when the electron-donating ability of the substituents is increased, while it becomes large when the electron-withdrawing ability of the substituents is increased. Subsequently, we consider the solvent effects on the reaction adding ethylene to the simplified hydrogen-substituted nickel dithiolene. It is found that the solvents will make slight changes to the geometries of the reactants, transition states, intermediates and products. However, the corresponding molecular dipole moments become large with the increase of the solvent polarity, which is beneficial to accelerate the reaction. Moreover, we show that, as the solvent polarity becomes large, the activation energies of the reaction decrease exponentially, while the reaction rate constants increase exponentially. These results demonstrate that in polar solvents, the reaction complexing ethylene with Ni dithiolene may become easier and faster to occur, and the product rate is improved. We believe that this research can be seen as a reference for complex and solvent selection in olefin separation process.
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]	BASIS-SETS ; DENSITY ; SEPARATION ; OLEFINS ; ENERGY ; THERMOCHEMISTRY ; REACTIVITIES ; CLUSTERS ; ALKENES ; CORE
收录类别	SCI
原文出处	://WOS:000258383800005
语种	英语
WOS记录号	WOS:000258383800005
公开日期	2013-10-08
内容类型	期刊论文
版本	出版稿
源URL	[http://ir.ipe.ac.cn/handle/122111/2758]
专题	过程工程研究所_研究所（批量导入）
作者单位	1.Chinese Acad Sci, Inst Proc Engn, Multiphase React Lab, Beijing, Peoples R China 2.Chinese Acad Sci, Grad Univ, Beijing, Peoples R China
推荐引用方式 GB/T 7714	Han, Qing-Zhen,Zhao, Yue-Hong,Wen, Hao. Quantum chemical study on influence of substituents and solvents in reaction complexing ethylene with nickel dithiolene[J]. MOLECULAR SIMULATION,2008,34(6):631-636.
APA	Han, Qing-Zhen,Zhao, Yue-Hong,&Wen, Hao.(2008).Quantum chemical study on influence of substituents and solvents in reaction complexing ethylene with nickel dithiolene.MOLECULAR SIMULATION,34(6),631-636.
MLA	Han, Qing-Zhen,et al."Quantum chemical study on influence of substituents and solvents in reaction complexing ethylene with nickel dithiolene".MOLECULAR SIMULATION 34.6(2008):631-636.

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