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Type: Artigo de periódico
Title: Intrinsic acidity of dimethylhalonium ions: Evidence for hyperconjugation in dimethylhalonium ylides in the gas phase
Author: Noronha, LA
Judson, TJL
Dias, JF
Santos, LS
Eberlin, MN
Mota, CJA
Abstract: The intrinsic acidity of dimethylhalonium ions has been determined, both by theoretical methods and by gas-phase reactions of the isolated ions with pyridine bases. The calculated geometry of the dimethylhalonium ions shows a bent Structure with the C-X-C angle decreasing in the order Cl > Br > I. Thermochemical calculations for the reaction of the diniethylhalonium ions with pyridine, 2,6-dimethylpyridine, and 2,6-di-tert-butylpyridine indicate that proton transfer, with the formation of the dimethylhalonium ylide is endothermic, whereas methyl transfer, with formation of methylhalide, is exothermic. The endothermicities for proton transfer are, nevertheless, dependent on the steric hindrance of the base. The bulkier the bases, the less endothermic the proton-transfer reaction is. Experimental gas-phase reactions support the calculations, showing that methyl transfer is the major reaction of dimethylchloronium and dimethyliodonium with pyridine, whereas proton transfer, as well as single electron transfer, is observed for the bulkier bases. The calculations also indicate that acidity increases in the order chloronium > bromonium > iodonium. NBO calculations predict that hyperconjugation with the sigma* carbon-halogen orbital plays a role in stabilizing the halonium ylide species in the gas phase.
Country: EUA
Editor: Amer Chemical Soc
Citation: Journal Of Organic Chemistry. Amer Chemical Soc, v. 71, n. 7, n. 2625, n. 2629, 2006.
Rights: fechado
Identifier DOI: 10.1021/jo052439l
Date Issue: 2006
Appears in Collections:Unicamp - Artigos e Outros Documentos

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