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题名: The density functional theory study on the 1,3-dipolar cycloaddition of carbon-methyl nitrone with acrlonitrile
作者: Sun, XM;  Wang, MH;  Liu, P;  Bian, WS;  Feng, DC;  Cai, ZT
关键词: density functional theory ;  1,3-dipolar cycloaddition ;  carbon-methyl nitrone ;  acrlonitrile ;  transition state theory
刊名: JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM
发表日期: 2004-06-22
DOI: 10.1016/j.theochem.2004.04.006
卷: 679, 期:1-2, 页:73-87
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Physical
研究领域[WOS]: Chemistry
英文摘要: Eight competing reaction pathways on the potential energy surface of C-methyl nitrone with acrlonitrile have been determined at the B3LYP/6-311++G** level using the density functional theory, and each of them, which has a double-peak-double-valley structure, consists of reactants, a prior complex, two transition states and two products. Accurate geometric structures, relative stabilities and harmonic vibrational frequencies of the stationary points have been investigated. The changes of enthalpy, entropy and Gibbs free energy for each reaction path are also calculated. The Boltzmann equilibrium distributions for the eight puckered envelope conformations have also been discussed qualitatively through the calculations of Gibbs free energy at 20-1000 K. The absolute rate constant calculation at the room temperature has been performed using conventional transition state theory, and as a result the most probable reaction path is determined. The exothermal energies of the possible reaction paths range from 26.11 to 51.75 kJ/mol. The first potential barrier heights vary from 72.28 to 105.62 kJ/mol while the barrier heights of isomerization vary from 1.37 to 17.05 kJ/mol. It is found that the formation of H-bond plays a critical role in the reaction. The intramolecular H-bond increases the stability of the trans-C-methyl nitrone, and the intermolecular H-bond between the C-methyl nitrone and acrlonitrile results in the formation of the prior complex, both of which reduce the reactivity of the title system. Moreover, the relative energies calculated by higher level computations, including the MP2, MP3, MP4SDQ, and QCISD(T) methods, are consistent with that obtained from the B3LYP method, which indicates that the B3LYP/6-311++G** level of theory can apply to this kind of systems. (C) 2004 Elsevier B.V. All rights reserved.
关键词[WOS]: STEREOSPECIFIC SYNTHESIS ;  CYCLO-ADDITIONS ;  DFT ;  REGIOSELECTIVITY ;  REGIOCHEMISTRY ;  DIPOLAROPHILES ;  DAUNOSAMINE ;  ACOSAMINE ;  ALLENES
语种: 英语
WOS记录号: WOS:000221986000010
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/139341
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Chinese Acad Sci, Inst Chem, State Key Lab Mol React Dynam, Beijing 100080, Peoples R China
2.Shandong Univ, Inst Theoret Chem, Jinan 250100, Peoples R China

Recommended Citation:
Sun, XM,Wang, MH,Liu, P,et al. The density functional theory study on the 1,3-dipolar cycloaddition of carbon-methyl nitrone with acrlonitrile[J]. JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM,2004,679(1-2):73-87.
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