MATRIX SPECTROSCOPY OF THE PROPARGYL RADICAL AND PROPARGYL PEROXYL RADICAL
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Date
2004
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Publisher
Ohio State University
Abstract
Using a hyperthermal nozzle that we have developed we have produced propargyl radical ($HC\equiv CCH_{2}$) from the pyrolysis of propargyl bromide and butyn nitrite. Matrix isolated IR spectra and linear dichroism spectra were recorded, and vibrational symmetries were assigned. Photoionization mass spectrometry also confirmed the formation of propargyl radical. This hot nozzle thermally decomposes organic precursors in a stream of Ar and produces roughly $10^{13}$ hydrocarbon radicals/pulse. Using time of flight mass spectrometry and matrix isolated IR spectroscopy we have also observed the bimolecular self reaction of propargyl to form benzene, $C_{3}H_{3} + C_{3}H_{3} \rightarrow C_{6}H_{6}$. IR spectra also show that the formation of $CH_{3}-C\equiv CH$ and $CH_{2}=C=CH_{2}$ occurs in the hyperthermal nozzle. Co-depositing the propagyl radical with molecular oxygen allows us to synthesize the propagyl peroxyl radical ($H-C\equiv C-CH_{2}OO$), which we have characterized in the infrared as well.
Description
Author Institution: Dept. Chemistry, University of Colorado Boulder; Dept. Chemistry, Center for Renewable Chemical Technologies \& Materials