INFRARED SPECTRA OF THE INTRAMOLECULAR HYDROGEN-BONDED DICHLORO- AND DIFLUORO-HALOFORM ANIONS IN SOLID ARGON

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1979

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Ohio State University

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The compounds $CHCl_{2} X$ and $CHF_{2} X$ (where X = F, Cl, Br, I) were subjected to argon resonance photoionization during condensation with excess argon at 15 K, and the products studied by infrared spectroscopy. The anion product in the dichlorohaloform experiments exhibits isotopic data appropriate for species of the type $Cl^{-}HCCl_{2}$, the intramolecular hydrogen-bonded parent anion. This species is produced upon electron capture by the parent molecule. The infrared spectrum containing $\nu_{s}, 2\nu_{b}, \nu_{b}$, and $\nu_{x}$ clearly demonstrates the effect of hydrogen bonding in $Cl{^{-}}-HCCl_{2}$, which decreases in the $Br^{-}-HCCl_{2}$ and $I^{-}-HCCl_{2}$ anions. In the difluorohaloform experiments, isotopic substitution data identify the $F-H--(CFX)^{-}$ and $X-H--(CF_{2})^{-}$ hydrogen-bonded parent anions. The bonding and photochemistry of these interesting anions will be discussed..

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