Intrinsic acidity of dimethylhalonium ions: evidence for hyperconjugation in dimethylhalonium ylides in the gas phase.
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 dimethylhalonium 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.
Universidade Federal do Rio de Janeiro, Instituto de Química, Departamento Química Orgânica, Cidade Universitaria CT Bloco A, 21949-900 Rio de Janeiro, Brazil.
Leandro A
LA
Noronha
Thiago J L
TJ
Judson
Jacques F
JF
Dias
Leonardo S
LS
Santos
Marcos N
MN
Eberlin
Claudio J A
CJ
Mota