Secondary kinetic isotope effects in bimolecular nucleophilic substitutions. III. Deuterium effects in the Bunte salt reaction of methyl halides and sulfonates

Secondary kinetic deuterium isotope effects have been measured for the reaction between thiosulfate ion and methyl-d 3 halides and sulfonates in 50% v/v ethanol-water. The results are used to extend the correlation of Seltzer of k H /k D with the difference between the polarizabilities of the attack...

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Bibliographic Details
Published in:Canadian journal of chemistry 1969-05, Vol.47 (9), p.1537-1541
Main Authors: Jackson, G. E, Leffek, K. T
Format: Article
Language:English
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Summary:Secondary kinetic deuterium isotope effects have been measured for the reaction between thiosulfate ion and methyl-d 3 halides and sulfonates in 50% v/v ethanol-water. The results are used to extend the correlation of Seltzer of k H /k D with the difference between the polarizabilities of the attacking nucleophile and the leaving group.Dissociation constants for the [NaS 2 O 3 ] − ion have been determined by conductivity measurements for the reaction conditions and used to calculate the concentration of free thiosulfate ions present in the reaction mixture. The activation parameters ΔH ≠ and ΔS ≠ , based on second order rate constants calculated with respect to the concentration of thiosulfate ion, are reported.
ISSN:0008-4042
1480-3291
DOI:10.1139/v69-253