Abstract
We report upon the direct detection of difluorocarbene following infrared multiphoton photolysis of pentafluoroethyl iodide using well-defined (SLM, TEM 00, 80 ns pulse width) TEA CO 2-laser pulses. The rate of appearance of CF 2 at 1 mTorr pressure and RRKM modelling of the unimolecular dissociation of C 2F 3I and C 2F 5 using reasonable input parameters are presented. These support a mechanism whereby CF 2 is produced by secondary photolysis of pentafluoroethyl radicals. Measurements of the velocity of CF 2 by the transient diffusion technique lead to an estimate of 2.6 kcal/mol for its average translational energy acquired from the homolytic cleavage of the CI and CC bonds. This value is higher than that predicted from the models using reasonable spontaneous dissociation rates ( = 10 9 s −1). An inherent assumption of the models is that the excess energy of dissociation is distributed statistically among the vibrational modes of the reaction complex and that there are no small barriers in the exit channel.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
