Unimolecular reactions of CH(2)BrCH(2)Br, CH(2)BrCH(2)Cl, and CH(2)BrCD(2)Cl: identification of the Cl-Br interchange reaction.

The recombination reactions of CH(2)Br and CH(2)Cl radicals have been used to generate vibrationally excited CH(2)BrCH(2)Br and CH(2)BrCH(2)Cl molecules with 91 kcal mol(-1) of energy in a room-temperature bath gas. The experimental unimolecular rate constants for elimination of HBr and HCl were compared to calculated statistical rate constants to assign threshold energies of 58 kcal mol(-1) for HBr elimination from C(2)H(4)Br(2) and 58 and 60 kcal mol(-1), respectively, for HBr and HCl elimination from C(2)H(4)BrCl. The Br-Cl interchange reaction was demonstrated and characterized by studying the CH(2)BrCD(2)Cl system generated by the recombination of CH(2)Br and CD(2)Cl radicals. The interchange reaction was identified from the elimination of HBr and DCl from CH(2)ClCD(2)Br. The interchange reaction rate is much faster than the rates of either DBr or HCl elimination from CH(2)BrCD(2)Cl, and a threshold energy of congruent with43 kcal mol(-1) was assigned to the interchange reaction. The statistical rate constants were calculated from models of the transition states that were obtained from density functional theory using the B3PW91 method with the 6-31G(d',p') basis set. The model for HBr elimination was tested versus published thermal and chemical activation data for C(2)H(5)Br. A comparison of Br-Cl interchange with the Cl-F and Br-F interchange reactions in 1,2-haloalkanes is presented.