Abstraction of chlorine atoms from chloroalkanes. V. The liquid-phase reaction between Et3SiH radicals and CH2Cl2, CHCl3, CCl4, and CCl3CN
✍ Scribed by R. Aloni; L. A. Rajbenbach; A. Horowitz
- Publisher
- John Wiley and Sons
- Year
- 1979
- Tongue
- English
- Weight
- 318 KB
- Volume
- 11
- Category
- Article
- ISSN
- 0538-8066
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✦ Synopsis
The kinetics of chlorine transfer from CHzC12, CHC13, cc4, and CCI3CN to the triethylsilyl radical was studied in the liquid phase by a competitive method. Br abstraction from 1- bromopentane was used as a reference. The following Arrhenius parameters were determined:
40 f 0.10 1.11 f 0.18 303-343 CHCls 0.28 f 0.16 0.19 f 0.28 273-423 cc14 1.25 f 0.28 -0.17 f 0.22 297-398 CClnCN 1.86 f 0.12 0.24 f 0.24 323-448
where the error limits are two standard deviations (2a). Based on these results, the observed reactivity trends in the chlorine transfer reactions of Et$i radicals appear to primarily reflect the variation in entropy of activation rather than in activation energies.