Journal of Physical Chemistry p. 3080 - 3084 (1991)
Update date:2022-08-17
Topics:
Bai, Hebi
Ault, Bruce S.
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.
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