A combination of experimental and theoretical work strongly implicates the production of vinylidene in the photodissociation of the allyl radical CH(2)CHCH(2), an important intermediate in hydrocarbon combustion. The evidence comes from a study of the dissociation of 2-d(1)-allyl, which yields distinctly different, translational energy distributions and mechanisms for the products HCCH + CH(2)D and DCCH + CH(3). In one mechanism a 1,3 hydrogen shift takes place to given the CH(2)CDCH intermediate, which then dissociates to yield CH(3) + DCCH, whereas in the second, one of two branches occurs after a 1,2 hydrogen shift. The shift forms CH(2)D-C-CH(2), which either dissociates directly to CH(2)D + CCH(2) (vinlyidene) or undergoes a second 1, 2 shift to give CH(2)D-CH-CH, which subsequently dissociates to CH(2)D + HCCH.

Evidence for Vinylidene Production in the Photodissociation of the Allyl Radical / Chao, Chen; Bastiaan, Braams; David Y., Lee; Joel M., Bowman; Paul L., Houston; Stranges, Domenico. - In: THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS. - ISSN 1948-7185. - STAMPA. - 1:12(2010), pp. 1875-1880. [10.1021/jz100638v]

Evidence for Vinylidene Production in the Photodissociation of the Allyl Radical

STRANGES, Domenico
2010

Abstract

A combination of experimental and theoretical work strongly implicates the production of vinylidene in the photodissociation of the allyl radical CH(2)CHCH(2), an important intermediate in hydrocarbon combustion. The evidence comes from a study of the dissociation of 2-d(1)-allyl, which yields distinctly different, translational energy distributions and mechanisms for the products HCCH + CH(2)D and DCCH + CH(3). In one mechanism a 1,3 hydrogen shift takes place to given the CH(2)CDCH intermediate, which then dissociates to yield CH(3) + DCCH, whereas in the second, one of two branches occurs after a 1,2 hydrogen shift. The shift forms CH(2)D-C-CH(2), which either dissociates directly to CH(2)D + CCH(2) (vinlyidene) or undergoes a second 1, 2 shift to give CH(2)D-CH-CH, which subsequently dissociates to CH(2)D + HCCH.
2010
01 Pubblicazione su rivista::01a Articolo in rivista
Evidence for Vinylidene Production in the Photodissociation of the Allyl Radical / Chao, Chen; Bastiaan, Braams; David Y., Lee; Joel M., Bowman; Paul L., Houston; Stranges, Domenico. - In: THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS. - ISSN 1948-7185. - STAMPA. - 1:12(2010), pp. 1875-1880. [10.1021/jz100638v]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/50028
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