Experimental and Computational Studies of Unimolecular 1,1-HX (X = F, Cl) Elimination Reactions of CDCHFCl: Role of Carbene:HF and HCl Adducts in the Exit Channel of RCHFCl and RCHCl Reactions.

The gas-phase unimolecular reactions of CDCHFCl molecules with 94 kcal mol of vibrational energy have been studied by the chemical-activation experimental technique and by electronic-structure computations. Products from the reaction of CDCHFCl molecules, formed by the recombination of CD and CHFCl radicals in a room temperature bath gas, were measured by gas chromatography-mass spectrometry. The 2,1-DCl (81%) and 1,1-HCl (17%) elimination reactions are the principal processes, but 2,1-DF and 1,1-HF elimination reactions also are observed.