Ja. Harrison et H. Frei, VISIBLE LIGHT-INDUCED OXYGEN-TRANSFER FROM NITROGEN-DIOXIDE TO ETHYNEAND PROPYNE IN A CRYOGENIC MATRIX .1. IDENTIFICATION OF PRODUCTS, Journal of physical chemistry, 98(47), 1994, pp. 12142-12151
Photochemical reaction of ethyne.NO2 and propyne.NO2 pairs isolated in
solid Ar has been observed at wavelengths as long as 582 nm (HC=CH.NO
2) and 615 nm(CH3C=CH.NO2). Continuous wave dye laser radiation was us
ed to excite the reactants, and the chemistry was monitored by FT-infr
ared spectroscopy. In the case of ethyne + NO2, the sole products were
CH2=C=O and NO. The reaction of NO2 with propyne gave methylketene pl
us a trapped intermediate, CH3C(=NO.)C(=O)H (formyl methyl iminoxy rad
ical). Infrared spectra of this radical are reported for the first tim
e. Product identification was based on D, O-18, and N-15 isotopic subs
titution. Selective interconversion with tuned visible laser light rev
ealed the presence of four conformers, most probably originating from
isomerism about the C-C and the C=N bonds. Photoelimination of NO from
the iminoxy radical was observed at wavelengths as long as 625 nm. Pr
opynol and methylketene could be identified among the secondary photol
ysis products.