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Laser-induced reactions of hexafluorobenzene and selected hydride compounds

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100286a014· OSTI ID:7100923
; ;
Infrared-laser-induced reactions between C/sub 6/F/sub 6/ and general hydrides R-H (R = H, D, CH/sub 3/, HC triple bond C, H/sub 2/C double bond CH, and Cl) were studied by irradiating C/sub 6/F/sub 6/ at 1027 cm/sup -1/ in C/sub 6/F/sub 6//R-H mixtures. In general, two competitive pathways involving C-F bond cleavage in C/sub 6/F/sub 6/ were observed as follows: (1) C/sub 6/F/sub 6/ + R-H ..-->.. C/sub 6/F/sub 5/H + R-F and (2) C/sub 6/F/sub 6/ + %-H ..-->.. C/sub 6/F/sub 5/R + HF. C/sub 6/F/sub 6/ decomposition also took place to a minor extent depending on the mole fraction of C/sub 6/F/sub 6/ and gave rise to C/sub 2/F/sub 4/ and C/sub 2/H/sub 2/. When D/sub 2/ was used C/sub 6/F/sub 5/D was the major product. C/sub 6/F/sub 5/H was the major product in the reactions involving H/sub 2/ and C/sub 2/H/sub 2/. Besides C/sub 6/F/sub 5/H, other monosubstituted products derived from C/sup 6/F/sup 6/ were also formed, generally within 20-100 pulses. Thus, C/sub 6/F/sub 5/CH/sub 3/, C/sub 6/F/sub 5/CH double bond CH/sub 2/, CH/sub 2/, C/sub 6/F/sub 5/C triple bond CH, and C/sub 6/F/sub 5/Cl were produced, respectively in the reaction of C/sub 6/F/sub 6/ with CH/sub 4/, C/sub 2/H/sub 4/, C/sub 2/H/sub 2/, and HCl. In the first and last cases these products were the major ones observed. The results are discussed mechanistically in terms of the initial formation of the C/sub 6/F/sub 5/ radical and synthetically in terms of the utility of obtaining selective laser-induced reduction of C/sub 6/F/sub 6/.
Research Organization:
Brandeis Univ., Waltham, MA
OSTI ID:
7100923
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 91:2; ISSN JPCHA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
400500* -- Photochemistry
ACETYLENE
ALKANES
ALKENES
ALKYNES
AROMATICS
BENZENE
CARBON DIOXIDE LASERS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DEUTERIDES
DEUTERIUM COMPOUNDS
ELEMENTS
ETHYLENE
EXPERIMENTAL DATA
GAS LASERS
HYDROCARBONS
HYDROCHLORIC ACID
HYDROGEN
HYDROGEN COMPOUNDS
HYDROGEN DEUTERIDE
INFORMATION
INFRARED SPECTRA
INORGANIC ACIDS
LASERS
METHANE
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PULSE TECHNIQUES
SPECTRA