Thermochemical determination of the structure of negative ions on the basis of data from resonance electron capture mass spectrometry. Phenol, its chlorinated derivatives and a thioanalogue
Appearance energies for [M - H](-) ions from phenol (I), 4-chlorophenol (II), pentachlorophenol (III) and pentachlorothiophenol (IV) were measured. The following thermochemical data were deduced from experiment: DeltaH(acid) values of 343.3, 335.7, 317.1 and 317.1 kcal mol(-1) for RH molecules (I, II, III, and IV, respectively) and electron affinities (EAs) of R(.) free radicals 2.55, 2.90, 3.79, and 3.65 eV, respectively. Our data for phenol (I) and 4-chlorophenol (II) demonstrate a higher stabilization of ArO(-) anions than was previously accepted. Using the enthalpic shift procedure for molecules and a series of isodesmic reactions for free radicals, earlier elaborated by the authors, a new Delta$bf H_bf fbf 0$ values for the following gas-phase species were obtained (kcal mol(-1)): C(6)Cl(5)Br (5.0), C(6)Cl(5)SH (8.5), p-ClC(6)H(4)C(.) (2. 0), C(6)Cl(5)C(.) (-15), C(6)Cl(5)S(.) (44). Copyright 2000 John Wiley & Sons, Ltd.
Institute of Physics of Molecules and Crystals, Ufa Research Centre, Russian Academy of Sciences, 151 Prospect Oktiabrya, 450075, Ufa, Russia.
MV
Muftakhov
RV
Khatymov
VA
Mazunov
DA
Ponomarev
VV
Takhistov
LP
Vatlina