We have collected low-temperature IR spectra of CH3CN�Cl2 and CH3CN�ClF, both in argon matrices and matrix-free, bulk thin films. The measured frequencies for CH3CN�Cl2 differ only marginally from the computed gas-phase values, but systematic shifts are observed for the interhalogen stretching frequency of CH3CN�ClF across various media. Computational investigations of the N-Cl potentials in the gas phase and in dielectric media indicate that Cl2 complex is weak and relatively insensitive to solvent effects, but the minimum on the CH3CN�ClF potential does shift inward by 0.2 � at e=6. We also found that CH3CN and Cl2 exhibited no reactivity at room temperature, but observed a solid product at temperatures below -10�C. Acetonitrile and ClF combine to form a yellowish liquid at room temperature, and a solid also appears at -10�C. Attempts to obtain crystallographic structures of these products are in progress.

Condensed-phase effects on the structural properties of CH3CN-Cl2 and CH3CN-ClF: IR spectra, computations, and bulk reactivity

239th National Meeting (2010)

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