Premium
The reactions of CF 3 and CD 3 radicals with boron trimethyl
Author(s) -
Bell T. N.,
Platt A. E.
Publication year - 1971
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550030403
Subject(s) - chemistry , radical , arrhenius equation , hydrogen atom abstraction , boron , molecule , photochemistry , photodissociation , hydrogen , atmospheric temperature range , polar , computational chemistry , medicinal chemistry , organic chemistry , activation energy , thermodynamics , physics , astronomy
Hydrogen abstraction from boron trimethyl has been studied using the abstracting radicals CF 3 and CD 3 , from the photolysis of the corresponding ketones over the temperature range of 150° to 300°C. The following Arrhenius parameters were obtained:\documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} {\rm (CD}_{\rm 3} {\rm + BME}_{\rm 3} {\rm); log }A{\rm = 11}{\rm .8, }E{\rm = 9}{\rm .98 kcal/mole} \\ {\rm (CF}_{\rm 3} {\rm + BMe}_{\rm 3} {\rm); log }A{\rm = 11}{\rm .6, }E{\rm = 6}{\rm .59 kcal/mole} \\ \end{array}$$\end{document}The difference E CD 3– E CF 3in the case of BMe 3 is considered due, in part, to polar effects. An exchange reaction is proposed for both CF 3 and CD 3 in collisions with BMe 3 :\documentclass{article}\pagestyle{empty}\begin{document}$${\rm R} + {\rm B}({\rm Me})_3 \to {\rm Me} + {\rm RBMe}_2$$\end{document}Radical combination of CF 3 and CH 2 BMe 2 leads to a hot molecule which undergoes a β‐fluoro rearrangement elimination process, or a stabilized molecule which can thermally decompose: