Tetrafluorobenzyne thermochemistry: experiment and theory |
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Authors: | Pratt Lawrence M Fattahi Alireza Kass Steven R |
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Affiliation: | Department of Chemistry, Fisk University, Nashville, TN 37208, USA. |
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Abstract: | Gas-phase thermodynamic properties of 1,2,3,4-tetrafluorobenzyne (1 H-(2)) were determined by Fourier transform mass spectrometry and ab initio and density functional theory methods. 1,2,3,4-Tetrafluorobenzyne radical anion was generated by abstraction of a proton and a hydrogen atom upon reaction of 1,2,3,4-tetrafluorobenzene (1) with O(-.). The resulting structure was confirmed by converting it to a species which could be independently prepared. Bracketing results provided the proton affinity of 1,2,3,4-tetrafluorobenzyne radical anion and the electron affinities of 1,2,3,4-tetrafluorobenzyne and 1,2,3,4-tetrafluorophenyl radical. These measured values were combined in a thermodynamic cycle to provide the heat of hydrogenation of 1 H(2) (DeltaH degree (hyd) = 367 +/- 18 kJ mol(-1)) and the first and second CH bond dissociation energies of 1 (481 +/- 11 and 321 +/- 13 kJ mol(-1)). The same approach failed for the meta and para isomers, but their energetics were examined using B3LYP and CCSD(T) computations. |
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