STRUCTURE, DYNAMICS AND VIBRATIONAL-SPECTRA OF ALPHA-CHLOROALLYL CATIONS IN SOLID SBF5-MATRICES

Cis- and trans-alpha-chloroallyl cations were prepared by matrix isola tion method in solid SbF5 matrix, and obtained FT-IR spectra compared with the results of high-level ab-initio calculations. Ionization of e ither cis- or trans-1,3-dichloropropenes lead to the mixture of cis- a nd trans-cations, whose interconversion barrier is smaller than for pa rent allyl cation. The extent of alpha-chlorine carbocation stabilizat ion was shown to be comparable to that obtained by methyl group. Addit ionally, the ionization constant of chloropropenes in the solid SbF5, matrix was measured for the first time.