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Study of halogen exchange in allyltin trihalides by two-dimensional 119Sn EXSY NMR

✍ Scribed by Isabelle Pianet; Eric Fouquet; Michel Pereyre; Marcel Gielen; François Kayser; Monique Biesemans; Rudolph Willem

Publisher
John Wiley and Sons
Year
1994
Tongue
English
Weight
541 KB
Volume
32
Category
Article
ISSN
0749-1581

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✦ Synopsis

Abstract

(2‐Ethoxycarbonyl)crotylbromodichlorostannane (1) and (2‐ethoxycarbonyl)allylbromodichlorostannane (2), two compounds with formula RSnCl~2~Br, were shown by 2D phase‐sensitive EXSY ^119^Sn NMR to undergo halogen exchange, resulting in equilibrium mixtures of RSnCl~3~, RSnCl~2~Br, RSnClBr~2~ and RSnBr~3~. The unidirectional pseudo‐first‐order rate constants were determined by two different methods, the initial rate and the exchange matrix resolution approaches. The data show that the exchange proceeds by single halogen exchange, probably occurring through an intermediate involving two organotin trihalide moieties, as evidenced from the linear dependence of the pseudo‐first‐order rate constants on concentration. The mechanism is briefly discussed.

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