1,2-H SHIFT IN BENZYLCHLOROCARBENE - ISOTOPE EFFECT AND INFLUENCE OF THE SOLVENT

被引：21

作者：

LIU, MTH

BONNEAU, R

WIERLACHER, S

SANDER, W

机构：

[1] UNIV BORDEAUX 1,CNRS,UA 348,F-33405 TALENCE,FRANCE

[2] TECH UNIV CAROLO WILHELMINA BRAUNSCHWEIG,INST ORGAN CHEM,W-3300 BRAUNSCHWEIG,GERMANY

来源：

JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY | 1994年 / 84卷 / 02期

基金：

加拿大自然科学与工程研究理事会;

关键词：

D O I：

10.1016/1010-6030(94)03850-3

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Laser flash photolysis of 3-chloro-3-benzyldiazirine and 3-chloro-3-(phenyldideuteriomethyl)diazirine in isooctane over the 60 to -80-degrees-C temperature range gives rise to curved Arrhenius plots for both 1,2-H and 1,2-D migration in benzylchlorcarbene. The k(H)/k(D) values increase smoothly from 0.87 to 2.62 when the temperature increases from -60 to +30-degrees-C. The k(H)/k(D) value is approximately 4 for most of the temperatures studied if a solvent correction is applied. Quantum mechanical tunnelling or the influence of the solvent may be a possible explanation for these observations.

引用

页码：133 / 137

页数：5

共 25 条

[1] RATES FOR 1,2 MIGRATION IN ALKYLCHLOROCARBENES [J].