Infrared multiphoton dissociation of two perfluorobutenes
- Chemical Sciences Division, Lawrence Berkeley Laboratory, and Department of Chemistry, University of California, Berkeley, California 94720 (United States)
Photofragment translational spectroscopy was used to examine the infrared multiphoton dissociation of octafluoro-1-butene and octafluoro-2-butene. The predominant unimolecular reaction in octafluoro-1-butene at moderate laser fluences is cleavage of a carbon{endash}carbon single bond to give the products CF{sub 3} and C{sub 3}F{sub 5}. The two other reactions that take place are CF{sub 2} elimination and the formation of equal weight fragments with the chemical composition C{sub 2}F{sub 4}; both reactions take place via a diradical intermediate. Dissociation of octafluoro-1-butene to the resonance stabilized perfluoroallyl radical is suggested to account for the favoring of simple bond rupture. These three reaction pathways were also observed in octafluoro-2-butene dissociation, however, the branching fraction is different than from octafluoro-1-butene. In octafluoro-2-butene all three channels occur with roughly equal probability. The reactions involving CF{sub 2} loss and C{sub 2}F{sub 4} formation in octafluoro-2-butene are thought to proceed through the same diradical intermediate as in octafluoro-1-butene, necessitating a 1,2-fluorine migration. {copyright} {ital 1997 American Institute of Physics.}
- Research Organization:
- Lawrence Berkeley National Laboratory
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 544797
- Journal Information:
- Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 18 Vol. 107; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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