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• W2044762674 abstract "Abstract The infrared multiphoton laser induced reactions of hexafluorobenzene and related pentafluoro analogues (pentafluorobenzene, pentafluorochlorobenzene, pentafluorobromobenzene, and pentafluoroiodobenzene) have been investigated using a CO 2 TEA laser. The study was carried out in order to define the decomposition products and to attempt to clarify their mode of formation. Thus, the products (relative yield, %) of the irradiation of C 6 F 6 (1027.3 cm −1 ; 0.73.J/cm 2 ; 10 pulses; 25% decomposition) were C 2 F 4 (64), C 6 F 5 CF 3 (28), C 2 F 6 (7), CF 4 (1) and that for C 6 F 5 H (949.4 cm −1 ; 0.80 J/cm 2 ; 10 pulses; 25% decomposition) was C 2 F 4 and C 6 F 5 CF 3 . Increasing the number of pulses in the reaction with C 6 F 6 decreased the amount of C 2 F 4 and increased the amount of C 6 F 5 CF 3 and C 2 F 6 indicating secondary and tertiary reactions. Addition of halogen (X 2 , X = Cl, Br) to these reactions caused different products to be formed. Thus, the irradiation of a C 6 F 6 /Cl 2 mixture (7.4/7 Torr; 1027.3 cm −1 ; 0.7 J/cm 2 ; 35 pulses; 35% reaction) afforded C 6 F 5 Cl(46); CF 3 Cl(24) and CF 2 Cl 2 (30). Irradiation of C 6 F 5 H/X 2 mixtures afforded mainly C 6 F 5 X + HX. For example, C 6 F 5 H/Br 2 (10/40 Torr; 949.4 cm −1 ; 0.93 J/cm 2 ; 10 pulses; 10% reaction) gave C 6 F 5 Br and HBr exclusively. Irradiation of C 6 F 5 -X (X = Cl, Br, I) (977.2 cm −1 ; ca. 0.74 J/cm 2 ; 200 pulses, 39–74% reaction) gave C 6 F 6 and a minor amount of decafluorobiphenyl [(C 6 F 5 ) 2 ], a radical combination product of the pentafluorophenyl radical (C 5 F 5 ·). Increasing the fluence in these reactions gave similar produts in most cases but in some instances increased the amount of C 2 F 4 formed. The reactions and product distribution of the hydrogen substituted derivative (C 6 F 5 H) was examined in the presence of Br 2 as a function of laser fluence and halogen concentration. It was found that the threshold for C 6 F 5 H decomposition was higher for the reaction involving Br 2 (as compared with the reaction involving Cl 2 or neat C 6 F 5 H). The presence of Br 2 also decreased the amount of C 6 F 5 H that was decomposed, indicating a quenching process. The decomposition path with the lowest activation energy for these molecules is thought to be C 6 F 5 X→C 6 F 5 · + X· and was accessible using a laser pulse with a fluence as low as 0.7 J/cm 2 . Using a higher laser fluence ( ca. 1.2 J/cm 2 ) diand triatomic radicals were defined by spectroscopic identification of the ·CF and :CF 2 species. These reactions are discussed in light of the formation of the C 6 F 5 · radical during a primary, larser induced, process. Subsequent decomposition to smaller fragments, combination with other radicals or scavenging by added reagents also takes place depending on the reaction conditions." @default.
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• W2044762674 date "1990-01-01" @default.
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• W2044762674 title "Infrared laser induced decomposition of hexafluorobenzene and some monosubstituted derivatives. Intermediacy of the pentafluorophenyl radical" @default.
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• W2044762674 doi "https://doi.org/10.1016/0584-8539(90)80153-p" @default.
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