LOCAL ORBITAL GUIDE TO ALLOWED INTERCONVERSIONS OF C4H7+ IONS

被引：43

作者：

TRINDLE, C

SINANOGL.O

机构：

[1] Sterling Chemistry Laboratory, Yale University, New Haven

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1969年 / 91卷 / 15期

关键词：

D O I：

10.1021/ja01043a006

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A guide to adiabatic reaction pathways, parallel to the method of Hoffmann and Woodward but convenient for three-dimensional molecules of low symmetry, is developed in terms of localized molecular orbi tals. Calculations on the C4H7+ system illustrate the technique; several predictions are made. The syn-allyl carbinyl ion closes to cyclobutyl ion by a disrotatory motion. The cyclopropylcarbinyl cation rearranges to a nonplanar cyclobutyl ion by bending the exo-methylene toward a ring carbon. The CH bond at the formally charged carbon naturally assumes the axial position essential to a stable cyclobutyl ion. The protonated planar methylene cyclopropane may undergo a pseudorotation by conrotatory motion of the exo- and a ring methylene. A detailed description of derealization in these ions is given by a newly developed semiempirical local orbital analysis. © 1969, American Chemical Society. All rights reserved.

引用

页码：4054 / &

共 37 条

[21] SMALL-RING COMPOUNDS .23. THE NATURE OF THE INTERMEDIATES IN CARBONIUM ION-TYPE INTERCONVERSION REACTIONS OF CYCLOPROPYLCARBINYL, CYCLOBUTYL AND ALLYLCARBINYL DERIVATIVES [J].