Matrix Isolation Study of Complexation and Exchange Reactions of Molecular Halogens with tert-Butyl Halides

Article abstract of DOI:10.1021/j100161a024

The 1/1 molecular complexes of tert-butyl chloride and bromide with ClF, Cl2 and Br2 have been isolated and characterized in argon matrices following twin-jet deposition.Perturbed vibrational modes of the tert-butyl halide, including the carbon-halogen stretching and the CH3 rocking modes, were observed upon complex formation.For the ClF complexes, the red-shifted Cl-F stretching mode was observed as well.The twin-jet codeposition of (CH3)3Br with Cl2 and ClF led to the exchange reaction product (CH3)3CCl, despite the very short mixing time in these experiments.The single-jet codeposition of these pairs of reactants led to further reactions, forming tert-butyl fluoride in the ClF experiments and 1,2-dichloro-2-methylpropane in the reactions of (CH3)3CCl and (CH3)3CBr with Cl2.While the halogen-exchange reactions are very facile, these results support the intermediacy of molecular complexes during the reaction process.