DFT STUDY OF THE DIELS-ALDER REACTIONS BETWEEN ETHYLENE WITH BUTA-1,3-DIENE AND CYCLOPENTADIENE

被引：165
作者：
JURSIC, B
ZDRAVKOVSKI, Z
机构：
[1] Department of Chemistry, University of New Orleans, New Orleans
来源：
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2 | 1995年 / 06期
关键词：
D O I：
10.1039/p29950001223
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
A set of DFT methods (Xa, HFB, S-VWN, B-LYP, B-HandH and Becke3-LYP) has been used for the calculation of the transition states and energy barriers of the Diels-Alder reaction of ethylene with buta-1,3-diene and cyclopentadiene. The pure DFT methods overestimate the bond lengths, while the hybrid methods give values much-closer to those obtained by conventional ab initio methods. The ratio of the sigma-forming bonds to the pi-breaking bonds is in excellent correlation to the predicted electronic energy barriers for these reactions. The local spin density approximation (S-VWN) fails completely giving a negative value for the classical energy barrier height for the addition of ethylene to buta-1,3-diene. On the other hand, the vibrational adiabatic barrier heights predicted by B-LYP/6-31G(**) and the hybrid Becke3-LYP/6-31G(**) theoretical models are in excellent agreement with available experimental data for both reactions.
引用
收藏
页码：1223 / 1226
页数：4
相关论文
共 30 条
  • [1] Parr R.G., Yang W., Density Functional Theory of Atoms and Molecules, New York and Oxford, (1989)
  • [2] Density Functional Methods in Chemistry, (1991)
  • [3] Parr R.G., Ann. Rev. Phys. Chem., 34, (1983)
  • [4] Borman S., Chem. Eng. News, 68, (1990)
  • [5] Ziegler T., Chem. Rev., 91, (1991)
  • [6] Johnson B.G., Theoreticul Und Computational Chemistry: Density Functional Calculations
  • [7] Politzer P., Seminario J.M., Trends Phys. Chem., 3, (1992)
  • [8] Politzer P., Seminario J.M., Chem. Phys. Lett., 207, (1993)
  • [9] Politzer P., Seminario J.M., Concha M.C., Murray J.S., Theor. Chim. Acta., 85, (1993)
  • [10] Politzer P., Seminario J.M., Int. J. Quant. Chem., 26, (1992)
123