ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Kinetics of protonation of Li+, Na+, K+, and Cs+ salts of anthracene radical anions (A-·,Cat+) and dianions (A2-, 2Cat+) by MeOH and MeOD in tetrahydrofuran (THF) and dimethoxyethane (DME) led to the determination of the isotope effect (kH/kD) in the following reactions: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm MeOH(MeOD) + A}\bar \cdot {\rm,Cat}^{\rm + } \to MeO^ - {\rm,Cat}^{\rm + } {\rm + AH} \cdot {\rm (D)} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm (MeOH)}_{\rm 2} {\rm or (MeOD)}_{\rm 2} {\rm + A}\bar \cdot {\rm,Cat}^{\rm + } \to {\rm MeOH,MeO}^ - {\rm,Cat}^{\rm + } {\rm + AH} \cdot {\rm (D)} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm MeOH (MeOD) + A}^{{\rm 2 - }} {\rm,2Cat}^{\rm + } \to {\rm MeO}^ - {\rm,Cat}^{\rm + } {\rm + AH(D)}^{{\rm - 1}},{\rm Cat}^{\rm +} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm MeOH (MeOD) + (A,Cat}^{\rm + } {\rm,A}^{{\rm 2 - }} {\rm,Cat}^{\rm + }) \to {\rm MeO}^ - {\rm,Cat}^{\rm + } {\rm + A + AH(D)}^{\rm - },{\rm Cat}^{\rm +} $$\end{document}Studies of cation and solvent influence on the rate constants of these reactions and on the magnitude of the isotope effect permitted us to draw some conclusions about the structure of the pertinent transition states. It seems that only the tight A-·,Na+ pairs participate in the protonation, and on this basis the fraction of tight ion paris of A-·,Na+ in DME was estimated. Our results have been compared with data reported in the literature.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550070611
Permalink
