HYPERCONJUGATION AND HOMO-HYPERCONJUGATION IN THE 1-ADAMANTYL CATION - QUALITATIVE MODELS FOR GAMMA-DEUTERIUM ISOTOPE EFFECTS

被引:56
作者
SUNKO, DE
HIRSLSTARCEVIC, S
POLLACK, SK
HEHRE, WJ
机构
[1] RUDJER BOSKOVIC INST, YU-41001 Zagreb, YUGOSLAVIA
[2] UNIV CALIF IRVINE, DEPT CHEM, IRVINE, CA 92717 USA
关键词
D O I
10.1021/ja00515a002
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
An experimental and theoretical study of the modes of stabilization of the carbocation-like transition state in the solvolysis of 1-substituted adamantyl systems is presented. Experimental determination of β- and α-deuterium isotope effects are used as a probe for hyperconjugative and homohyperconjugative stabilization. Ab initio molecular orbital theory is utilized to examine these same stabilizing influences. Our findings indicate carbon-carbon hyperconjugative stabilization to be the major mode of cation stabilization in the adamantyl system. © 1979, American Chemical Society. All rights reserved.
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页码:6163 / 6170
页数:8
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