2264-21-3Relevant articles and documents
Amphlett, J. C.,Whittle, E.
, p. 2130 - 2142 (1968)
Kasper et al.
, p. 1827 (1965)
Amphlett, J. C.,Whittle, E.
, p. 2695 - 2701 (1967)
Competing pathways in the infrared multiphoton dissociation of hexafluoropropene
Longfellow,Smoliar,Lee,Lee,Yeh,Lin
, p. 338 - 344 (1997)
The infrared multiphoton dissociation of hexafluoropropene was studied by photofragment translational spectroscopy. Two primary channels and one secondary channel were identified. The predominant primary channel produces CF3CF or C2F4 and CF2, with the heavier species undergoing further dissociation to two CF2 fragments. A number of dissociation mechanisms are proposed for the elimination of CF2, including direct cleavage of the carbon - carbon double bond. In the second primary channel, a simple bond rupture reaction produces CF3 and C2F3. As expected, the translational energy distribution for this channel peaks near zero, indicating no exit barrier is present. The activation energy for this simple bond rupture is estimated to be 100-105 kcal/mol. The branching ratio, [CF2]/[CF3], between the two primary pathways is 4.0 ± 1.0.
Photoinduced Sulfur-Nitrogen Bond Rotation and Thermal Nitrogen Inversion in Heterocumulene OSNSO
Wu, Zhuang,Feng, Ruijuan,Xu, Jian,Lu, Yan,Lu, Bo,Yang, Tao,Frenking, Gernot,Trabelsi, Tarek,Francisco, Joseph S.,Zeng, Xiaoqing
, p. 1231 - 1234 (2018/02/09)
An exotic ternary S, N, O heterocumulene OSNSO in syn-syn (A) and syn-anti (B) conformations has been generated in the gas phase through flash vacuum pyrolysis of CF3S(O)NSO at 700 K. Upon visible light irradiation (570 ± 20 or 532 nm), both A and B, isolated in cryogenic matrices (N2, Ne, Ar, and Kr, a higher-energy anti-anti conformer (C). The reverse conformational transformation occurs either through S=N bond rotation (C to A and B) under visible light irradiation (400 ± 20 nm) at 2.8 K or through thermal nitrogen inversion (C to A) in the temperature range of 20-30 K, for which an exceptionally low activation barrier of 1.18 ± 0.07 kcal mol-1 has been experimentally determined.
Products of the ultraviolet photodissociation of trifluoroacetic acid and acrylic acid
Osborne, Michael C.,Li, Qiang,Smith, Ian W. M.
, p. 1447 - 1454 (2007/10/03)
The photodissociation of trifluoroacetic and acrylic acids by the ultraviolet light from a flashlamp has been investigated by measuring the relative yields of some of the major products by time-resolved infrared absorption using tunable, narrow band diode lasers. Yields of CO2 were measured both in the absence and presence of added O2. The former experiments measure the CO2 produced directly by decarboxylation of the acid, channel (2) below, the latter the sum of the yields from channels (1) and (2) since HOCO is rapidly converted to CO2. The yields of CO from the decarbonylation channel (3) have also been measured. For trifluoroacetic acid, the relative yields are found to be [HOCO]: [CO2]: [CO] = (0.28 ± 0.07): (0.61 ± 0.09): (0.11 ± 0.06) and, for acrylic acid, [HOCO]: [CO2]: [CO] = (0.32 ± 0.08): (0.37 ± 0.08) :(0.31 ± 0.09). The results are discussed in relation to the other, limited, measurements on the photodissociation of these acids and whether these three processes are likely to occur independently of one another.
Kinetic study of the reactions of CF3O2 radicals with Cl and NO
Louis, Florent,Burgess Jr., Donald R.,Rayez, Marie-Therese,Sawerysyn, Jean-Pierre
, p. 5087 - 5096 (2007/10/03)
Kinetic studies of the reactions CF3O2 + Cl and CF3O2 + NO were performed at room temperature in the gas phase using the discharge flow mass spectrometric technique (DFMS). The reactions were investigated under pseudo- first-order conditions with Cl or NO in large excess with respect to the CF3O2 radicals. The rate constant for the reaction CF3O2 + NO was measured at 298 K and the value of (1.6 ± 0.3) x 10-11 cm3 molecule-1 s-1 is in very good agreement with all previous values. For the reaction CF3O2 + Cl, we obtain a rate constant at 298 K of (4.2 ± 0.8) x 10-11 cm3 molecule-1 s-1 in excellent agreement with the only published value. Product analysis shows that this reaction occurs via the major reaction pathway CF3O2 + Cl → CF3O + ClO at room temperature. In addition, an ab initio theoretical study was performed to gain insights on the different postulated reaction pathways. There is a significant disagreement between experimental and ab initio values recommended for the formation enthalpies of CF2O, CF3O and related molecules produced in this system. Consequently, we provide self-consistent values of enthalpies based on isodesmic reactions for the CF3O2 + Cl reaction system using the G2, G2(MP2) and CBS-Q methods. These values are also compared with BAC-MP4 heats of formation calculated in this work.