GAS-PHASE NUCLEOPHILIC DISPLACEMENT-REACTIONS OF NEGATIVE-IONS WITH CARBONYL-COMPOUNDS

被引:203
作者
ASUBIOJO, OI [1 ]
BRAUMAN, JI [1 ]
机构
[1] STANFORD UNIV,DEPT CHEM,STANFORD,CA 94305
关键词
D O I
10.1021/ja00508a002
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The rates of a number of nucleophilic displacement reactions X-+ RCOY → Y-+ RCOX have been studied with pulsed ion cyclotron resonance spectroscopy, where X = F, Cl, CH3O, CN, SH; R = CH3, C2H5, (CH3)3CH, (CH3)3C, C6H5, CF3; Y = Cl, Br. The results suggest that the potential surfaces contain at least two minima separated by a barrier. The kinetic model is analyzed using RRKM theory, which provides an estimate of the barrier height. The estimated stability of the “tetrahedral intermediate” is examined critically in terms of ions of comparable structure. © 1979, American Chemical Society. All rights reserved.
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页码:3715 / 3724
页数:10
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