Vibrational Excitation of the Reaction between Vinyl Bromide and Fluorine in Solid Argon

Article abstract of DOI:10.1021/j100235a022

A number of unsuccessful attempts to induce bimolecular addition reactions with selective vibrational excitation in cryogenic solids are reported here: 1,3-butadiene with Cl2, ClF, Br2, I2, and XeF2; vinyl chloride with F2.One system, vinyl bromide with fluorine in solid argon, did respond by showing reaction product growth upon laser excitation at 3116, 3098, 1849, 1808, and 1605 cm^-1.Identification of reaction products suggests F2 addition across the double bond followed significantly by HF elimination but apparently without HBr elimination.Relative quantum yields display a monotonic dependence upon photon energy that is even more dramatic than that found earlier for the ethylene-fluorine reaction.Thus excitation of the C-H stretching modes either at 3116 or 3098 cm^-1 is 10² times more effective than excitation at 1849 or 1848 cm^-1 and 10³ times more effective than at 1605 cm^-1.