Kinetics and rate constants for the reaction of tri-n-butylgermanium hydride with methyl iodide and carbon tetrachloride. The combination of methyl and trichloromethyl radicals in solution.
✍ Scribed by D. J. Carlsson; K. U. Ingold; L. C. Bray
- Publisher
- John Wiley and Sons
- Year
- 1969
- Tongue
- English
- Weight
- 468 KB
- Volume
- 1
- Category
- Article
- ISSN
- 0538-8066
No coin nor oath required. For personal study only.
✦ Synopsis
The kinetics of the photoinitiated reductions of methyl iodide and carbon tetrachloride by tri-n-butylgermanium hydride in cyclohexane at 25°C have been studied and absolute rate constants have been measured. Rate constants for the combination of CH,. and CC1,. radicals are equal within experimental error and are also equal to the values found for the self-reactions of most non-polymeric radicals in low viscosity solvents, i.e. -1-3 x l o 9 M-1 sec-1.
Rate constants for hydrogen atom abstraction by CH,. and CCl,. radicals are both -1-2
x lo5 M-' sec-l. Tri-n-butyltin hydride is about 10-20 times as good a hydrogen donor to alkyl radicals as is tri-n-butylgermanium hydride.
The strength of the germanium-hydrogen bond, D(n-Bu,Ge-H) is estimated to be approximately 84 kcal/mole.