Reactions of Recoil Generated Chlorine-38 Atoms with 2,3-Dichlorohexafluoro-2-butene. Cis/Trans Isomerization Accompanying Chlorine for Chlorine Replacement
Gas-phase reactions of nuclear recoil generated chlorine-38 atoms with 2,3-dichlorohexafluoro-2-butene (2,3-DCHF2B) result predominantly in chlorine for chlorine substitution. The reaction proceeds with geometrical isomerization, and the resulting cis-trans branching ratios are dependent on the isomeric identity of the reactant and the concentration of inert diluent present. Mechanistic features responsible for the observed behavior are discussed in terms of both a thermal or near-thermal reaction path and a concurrent high-energy process which preferentially forms trans product from both cis and trans reactants. The rate for addition of near-thermal chlorine atoms to 2,3-DCHF2B relative to addition to ethylene was found to be ~0.018. © 1978, American Chemical Society. All rights reserved.
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