CONFORMATIONAL DEPENDENCE OF SECONDARY BETA-DEUTERIUM ISOTOPE EFFECTS

被引：51

作者：

DEFREES, DJ

HEHRE, WJ

SUNKO, DE

机构：

[1] UNIV CALIF IRVINE, DEPT CHEM, IRVINE, CA 92717 USA

[2] UNIV ZAGREB, ORGAN CHEM LAB, YU-41001 Zagreb, YUGOSLAVIA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1979年 / 101卷 / 09期

关键词：

D O I：

10.1021/ja00503a014

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The conformational dependence of secondary β-deuterium isotope effects on hypothetical reactions involving formation of the ethyl cation, ethyl radical, and ethyl anion from ethane has been investigated by means of ab initio molecular orbital theory. In all three systems the hyperconjugative componentof the calculated secondary isotope effect is found to closely follow a cos2 a relationship, a being the dihedral angle which theß CH bond makes with the vacant (half-filled or filled) orbital at the cation (radical or anion) center. © 1979, American Chemical Society. All rights reserved.

引用

页码：2323 / 2327

页数：5

共 30 条

[21] COMPARISON OF EXPERIMENTALLY DERIVED AND THEORETICALLY CALCULATED DERIVATIVES OF ENERGY KINETIC ENERGY AND POTENTIAL ENERGY FOR CO [J].