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Hydrogen Migration and Vinylidene Pathway for Formation of Methane in the 193 Nm Photodissociation of Propene: CH3CH=CH2 and CD3CD=CD2

Hydrogen Migration and Vinylidene Pathway for Formation of Methane in the 193 Nm Photodissociation of Propene: CH3CH=CH2 and CD3CD=CD2

Yi-Lei Zhao, Allan H Laufer, Joshua B Halpern, Askar Fahr

J Phys Chem A. 2007 Aug 30;111(34):8330-5.

PMID: 17685497

Abstract:

Photodissociation channels and the final product yields from the 193 nm photolysis of propene-h6 (CH(2)=CHCH(3)) and propene-d6 (CD(2)=CDCD(3)) have been investigated, employing gas chromatography, mass spectroscopy, and flame ionization (GC/MS/FID) detection methods. The yields of methane as well as butadiene relative to ethane show considerable variations when propene-h6 or propene-d6 are photolyzed. This suggests significant variances in the relative importance of primary photolytic processes and/or secondary radical reactions, occurring subsequent to the photolysis. Theoretical calculations suggest the potential occurrence of an intramolecular dissociation through a mechanism involving vinylidene formation, accompanied by an ethylenic H-migration through the pi-orbitals. This process affects the final yields of methane-h4 versus methane-d4 with respect to other products. The product yields from previous studies of the 193 nm photolysis of methyl vinyl ketone-h6 and -d6 (CH(2)=CHCOCH(3), CD(2)=CDCOCD(3)), alternative precursors for generating methyl and vinyl radicals, are compared with the current results for propene.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP1517528	Propene-d6		1517-52-8	Price
AP558203	Methane-d4		558-20-3	Price

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