MATRIX INFRARED SPECTRUM OF THE MONOIODO AND DIIODOMETHYL RADICALS
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Date
1971
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Ohio State University
Abstract
Simultaneous deposition of $CH_{2}IX$ (X =Br. I) and CHI with atomic lithium or sodium at high dilution in argon on a CsI window maintained at $15^{\circ} K$ has produced the monoiodo---and diiodomethyl radicals respectively for infrared spectroscopic study. Vibrational assignments are made to $\nu_{2}$ (the symmetric H-C-H valance angle bend), $\nu_{3}$ (the symmetric C-I stretch), and $\nu_{4}$ (the out of plane hydrogen bend) for $CH_{2} I$ and to $\nu_{4}$ the antisymmetric H wag) and $\nu_{5}$ (the antisymmetric C-I stretch) for $CHI_{2}$. These assignments are supported by the reactions of lithium and sodium with $CHDI_{2}$, $CD_{2}I_{2}$ and $CDI_{3}$ and are further substantiated by normal coordinate calculations. The unusually high C-I force constants in $CH_{2} I$ and $CHI_{2}$ indicate stabilization of the C-I bond. The large positive quartic term in the potential function for $\nu_{6}$ of $CH_{2} I$ is evidence for a planar radical.
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Author Institution: Department of Chemistry, University of Virginia