Russian Chemical Bulletin p. 2149 - 2154 (1998)
Update date:2022-08-11
Topics:
Murachev
Byrikhin
Nesmelov
Ezhova
Orlinkov
The interaction of tert-butyl chloride with aluminum bromide in methylene dibromide at -30 °C leads to the formation of two types of adducts, which give signals with δ 2.4 and 3.2 in the 1H NMR spectra in addition to that of free alkyl halide. These signals are attributed to a polarized complex (PC) and ion pair (IP), respectively. An excess of AlBr3 shifts the equilibria toward IP. The latter contains more AlBr3 than the polarized complex. Based on the spectral data, we calculated the limiting values of some equilibrium constants. The ability of AlBr3 to solvate counterions is consistent with the results of isobutylene polymerization under the action of the initiating Bu1Cl-AlBr3 system at different ratios of the starting concentrations [AlBr3]0/[Bu1Cl]0. An increase in this ratio results in both the acceleration of polymerization and an increase in the relative role of chain transfer reactions.
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