Correlation of gas-phase stability of bridgehead carbocations with rates of solvolysis and ab initio calculations

被引:41
作者
Abboud, JLM
Castano, O
Della, EW
Herreros, M
Muller, P
Notario, R
Rossier, JC
机构
[1] UNIV ALCALA DE HENARES, DEPT QUIM FIS, ALCALA DE HENARES, MADRID, SPAIN
[2] FLINDERS UNIV S AUSTRALIA, DEPT CHEM, BEDFORD PK, SA 5042, AUSTRALIA
[3] UNIV GENEVA, DEPT CHIM ORGAN, CH-1215 GENEVA, SWITZERLAND
关键词
D O I
10.1021/ja962319i
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The stability of bridgehead carbocations has been determined by Fourier transform ion cyclotron resonance spectroscopy (FT ICR) based on dissociative proton attachment (DPA) of bromides and alcohols. The stability of the ions correlates with the solvolytic reactivity of bridgehead derivatives over a rate range of 23 log units, and with theoretical calculations for hydride transfer of bridgehead hydrocarbons at the MP2/6-311G** level.
引用
收藏
页码:2262 / 2266
页数:5
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