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Study of halogen exchange in allyltin trihalides by two‐dimensional 119 Sn EXSY NMR
Author(s) -
Pianet Isabelle,
Fouquet Eric,
Pereyre Michel,
Gielen Marcel,
Kayser François,
Biesemans Monique,
Willem Rudolph
Publication year - 1994
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.1260321010
Subject(s) - chemistry , halogen , trihalide , reaction rate constant , equilibrium constant , crystallography , computational chemistry , stereochemistry , analytical chemistry (journal) , halide , kinetics , inorganic chemistry , organic chemistry , alkyl , physics , quantum mechanics
(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.