Unimolecular reactions of CF2ClCFClCH2F and CF2ClCF2CH2Cl: observation of ClF interchange.

The unimolecular reactions of CF(2)ClCFClCH(2)F and CF(2)ClCF(2)CH(2)Cl molecules formed with 87 and 91 kcal mol(-1), respectively, of vibrational energy from the recombination of CF(2)ClCFCl with CH(2)F and CF(2)ClCF(2) with CH(2)Cl at room temperature have been studied by the chemical activation technique. The 2,3- and 1,2-ClF interchange reactions compete with 2,3-ClH and 2,3-FH elimination reactions. The total unimolecular rate constant for CF(2)ClCF(2)CH(2)Cl is 0.54 +/- 0.15 x 10(4) s(-1) with branching fractions for 1,2-ClF interchange of 0.03 and 0.97 for 2,3-FH elimination. The total rate constant for CF(2)ClCFClCH(2)F is 1.35 +/- 0.39 x 10(4) s(-1) with branching fractions of 0.20 for 2,3-ClF interchange, 0.71 for 2,3-ClH elimination and 0.09 for 2,3-FH elimination; the products from 1,2-ClF interchange could be observed, but the rate constant was too small to be measured. The D(CH(2)F-CFClCF(2)Cl) and D(CH(2)Cl-CF(2)CF(2)Cl) were evaluated by calculations for some isodesmic reactions and isomerization energies of CF(3)CFClCH(2)Cl as 84 and 88 kcal mol(-1), respectively; these values give the average energies of formed molecules at 298 K as noted above. Density functional theory was used to assign vibrational frequencies and moments of inertia for the molecules and their transition states. These results were combined with statistical unimolecular reaction theory to assign threshold energies from the experimental rate constants for ClF interchange, ClH elimination and FH elimination. These assignments are compared with results from previous chemical activation experiments with CF(3)CFClCH(2)Cl, CF(3)CF(2)CH(3,) CF(3)CFClCH(3) and CF(2)ClCF(2)CH(3).