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

被引：166

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

页码：1223 / 1226

页数：4

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