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. Comparison of experimental rate constants to calculated statistical rate constants provides threshold energies. The potential surfaces associated with CD(F)C: + HCl and CD(Cl)C: + HF reactions are of special interest because hydrogen-bonded adducts with HCl and HF with dissociation energies of 6.4 and 9.3 kcal mol, respectively, are predicted by calculations. The relationship between the geometries and threshold energies of transition states for 1,1-HCl elimination and carbene:HCl adducts is complex, and previous studies of related molecules, such as CDCHFCl, CDClCHFCl, CDCHCl, and halogenated methanes are included in the computational analysis. Extensive calculations for CHCHFCl as a model for 1,1-HCl reactions illustrate properties of the exit-channel potential energy surface. Since the 1,1-HCl transition state is submerged relative to dissociation of the adduct, inner and outer transition states should be considered for analysis of rate constants describing 1,1-HCl elimination and addition reactions of carbenes to HCl.