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Chemically activated C2D5CHCl2 molecules were generated with 88 kcal mol–1 of vibrational energy by the recombination of C2D5 and CHCl2 radicals in a room temperature bath gas. The competing 2,1-DCl and 1,1-HCl unimolecular reactions were identified by the observation of the CD3CD═CHCl and CD3CD═CDCl products. The initial CD3CD2C—Cl carbene product from 1,1-HCl elimination rearranges to CD3CD═CDCl under the conditions of the experiments. The experimental rate constants were 2.7 × 107 and 0.47 × 107 s–1 for 2,1-DCl and 1,1-HCl elimination reactions, respectively, which corresponds to branching fractions of 0.84 and 0.16. The experimental rate constants were compared to calculated statistical rate constants to assign threshold energies of 54 and ≈66 kcal mol–1 for the 1,2-DCl and 1,1-HCl reactions, respectively. The statistical rate constants were obtained from models developed from electronic-structure calculations for the molecule and its transition states. The rate constant (5.3 × 107 s–1) for the unimol...