Unimolecular isomerization of CH2FCD2Cl via the interchange of Cl and F atoms: assignment of the threshold energy to the 1,2-dyotropic rearrangement.

The room-temperature gas-phase recombination of CH2F and CD2Cl radicals was used to prepare CH2FCD2Cl molecules with 91 kcal mol(-1) of vibrational energy. Three unimolecular processes are in competition with collisional deactivation of CH2FCD2Cl; HCl and DF elimination to give CHF═CD2 and CH2═CDCl plus isomerization to give CH2ClCD2F by the interchange of F and Cl atoms. The Cl/F interchange reaction was observed, and the rate constant was assigned from measurement of CHCl═CD2 as a product, which is formed by HF elimination from CH2ClCD2F. These experiments plus previously published results from chemically activated CH2ClCH2F and electronic structure and RRKM calculations for the kinetic-isotope effects permit assignment of the three rate constants for CH2FCD2Cl (and for CH2ClCD2F). The product branching ratio for the interchange reaction versus elimination is 0.24 ± 0.04. Comparison of the experimental rate constant with the RRKM calculated rate constant permitted the assignment of a threshold energy of 62 ± 3 kcal mol(-1) for this type-1 dyotropic rearrangement. On the basis of electronic structure calculations, the nature of the transition state for the rearrangement reaction is discussed. The radical recombination reactions in the chemical system also generate vibrationally excited CD2ClCD2Cl and CH2FCH2F molecules, and the rate constants for DCl and HF elimination were measured in order to confirm that the photolysis of CD2ClI and (CH2F)2CO mixtures was giving reliable data for CH2FCD2Cl.

QTAIM analysis of the HF, HCl, HBr, and HOH elimination reactions of halohydrocarbons and halohydroalcohols.

The 1,2-HX elimination reaction (where X = F, Cl, Br, OH) has been established as an important reaction in the degradation of compounds introduced into the upper atmosphere, including common CFC replacement compounds. By analyzing the electron densities of the transition state geometries of these reactions using QTAIM, we see that we can divide these reactions into two types. For HF and HOH elimination, the transition state is a complete ring of bonds, and neither the C-H nor the C-X bonds have been broken at the maximum of energy. There is very little accumulation of electron density on the X atom, with the majority of charge being lost by the hydrogen atom undergoing elimination, being transferred on to the two carbon atoms. In HCl and HBr elimination, a similar loss of electron density of the hydrogen atom is accompanied by significant accumulation of electron density on the X atom and a smaller change in electron density on the carbon atoms. The C-X bond is broken in the transition state geometry, with no ring critical point being present. This may explain the relative stabilities of halohydrocarbons and haloalcohols with respect to loss of H-X.