Unimolecular reactions of vibrationally excited CF2ClCHFCH3 and CF2ClCHFCD3:: Evidence for the 1,2-FCl interchange pathway

Chemically activated CF2ClCHFCH3 and CF2ClCHFCD3 molecules were prepared with 94 kcal mol(-1) of vibrational energy by the recombination of CF2ClCHF and CH3(CD3) radicals at room temperature. The unimolecular reaction pathways were 2,3-FH(FD) elimination, 1,2-ClF interchange and 1,2-ClH elimination; the interchange produces CF3CHClCH3(CF3CHClCD3) with 105 kcal mol(-1) of vibrational energy. Rate constants for CF2ClCHFCH3 [CF2ClCHFCD3] were (3.1 +/- 0.4) x 10(6) s(-1) [(1.0 +/- 0.1) x 10(6) s(-1)] for 2,3-FH [FD] loss, (1.5 +/- 0.2) x 10(6) s(-1) [(8.3 +/- 0.9) x 10(5) s(-1)] for 1,2-ClF interchange, and (8.2 +/- 1.0) x 10(5) s(-1) [(5.3 +/- 0.6) x 10(5) s(-1)] for 1,2-ClH [DCl] loss. These correspond to branching fractions of 0.55 +/- 0.06 [0.43 +/- 0.04] for 2,3-FH [FD] loss, 0.29 +/- 0.03 [0.35 +/- 0.04] for 1,2-ClF interchange, and 0.16 +/- 0.02 [0.22 +/- 0.02] for 1,2-ClH [ClD] loss. Kinetic-isotope effects were 3.0 +/- 0.6 for 2,3-FH [FD] loss, 1.6 +/- 0.3 for 1,2-ClH loss, and 1.8 +/- 0.4 for 1,2-ClF interchange. The CF3CHClCH3 (CF3CHClCD3) molecules formed by 1,2-FCl interchange react by loss of HCl [DCl] with rate constants of (5.6 +/- 0.9) x 10(7) s(-1) [(2.1 +/- 0.4) x 10(7)] s(-1) for an isotope effect of 2.7 +/- 0.4. Density functional theory was employed to calculate vibrational frequencies and moments of inertia for the molecules and for the transition-state structures. These results were used with RRKM theory to assign threshold energies from comparison of computed and experimental unimolecular rate constants. The threshold energy for ClF interchange is 57.5 kcal mol(-1), and those for HF and HCl channels are 2-5 kcal mol(-1) higher. Experiments with vibrationally excited CF2ClCF2CF3, CF2ClCF2CF2Cl, and CF2ClCF2Cl, which did not show evidence for ClF interchange, also are reported.