RATE CONSTANTS FOR THE ADDITION OF THE 2-HYDROXY-2-PROPYL RADICAL TO ALKENES IN SOLUTION

被引:47
作者
HEBERGER, K
FISCHER, H
机构
[1] UNIV ZURICH,INST PHYS CHEM,WINTERTHURERSTR 190,CH-8057 ZURICH,SWITZERLAND
[2] HUNGARIAN ACAD SCI,CENT RES INST CHEM,H-1525 BUDAPEST,HUNGARY
关键词
D O I
10.1002/kin.550251105
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
Absolute rate constants for the addition of the 2-hydroxy-2-propyl radical to 18 substituted alkenes (CH2 = CXY) were determined at (296 +/- 1) K in 2-propanol by time-resolved electron-spin-resonance spectroscopy. With alkene substitution the rate constants vary by more than 6 orders of magnitude. For 3,3-dimethyl-but-1-ene the temperature dependence is given by log k/M-1 . s-1 = 6.4 - 19.1/THETA where THETA = 2.303 RT in kJ/mol-1. As shown by a good correlation with the alkene electron affinities, log k296/M-1 . s-1 = 6.46 + 1.71 - EA/eV (r = 0.930), 2-hydroxy-2-propyl is a very nucleophilic radical, and its addition rates are highly governed by polar effects. (C) 1993 John Wiley & Sons, Inc.
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页码:913 / 920
页数:8
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