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| - Mechanisms of Formation of Vinoxy Radicals in the Reaction of O(3P) with TerminalAlkenes
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| - When an O(3P) atom reacts with a terminal alkene, RCHCH2, a vinoxy radical can be produced by one oftwo mechanisms: (a) attachment of the oxygen atom to C1 followed by migration of a hydrogen atom fromC1 to C2 and then release of the radical R, or (b) attachment of the oxygen atom to C2 followed or accompaniedby release of the radical R. The hot band B ← X spectra of partially deuterated vinoxys allow one to distinguishbetween these two possibilities. The general result is that vinoxy is produced in comparable amounts by thetwo mechanisms. In the reaction of O(3P) atoms with ethylene, one of the product channels is a vinoxy anda hydrogen atom. A hydrogen atom can be directly released from the carbon atom to which the oxygen isattached or it can migrate to the other carbon forming a hot acetaldehyde. The latter then dissociates to formmethyl and formyl radicals (mainly) or a hydrogen atom and a vinoxy radical. The hot band spectra of vinoxysfrom the reaction of O(3P) with CHDCHD and CH2CD2 show that while both processes occur, the majorityof the hydrogen atoms are released directly rather than indirectly. Fast hydrogen atoms produced by photodissociation of H2S were shown to abstract a hydrogen atom from the methyl group of acetaldehyde yieldinga hydrogen molecule and vinoxy. The vinoxy is vibrationally very cold despite the large available energy.
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