Thermochemical Properties of the Benzynes

Abstract

The thermochemical properties of the benzynes have been the subject of investigation for nearly 50 years. This work provides an overview and assessment of all the experimental thermochemical properties that have been reported for the benzynes, or can be derived from reported thermochemical data. These properties include enthalpies of formation and thermochemical values that correspond to formation and dissociation of the benzynes by neutral and ionic processes. Thermochemical values are provided for both the ground-state singlet and the excited-state triplet states of the benzynes. The starting point for all the thermochemical consideration of the benzynes are the enthalpies of formation, which, in this work, are recommend to be 107.3 ± 3.5, 121.9 ± 3.1, and 138.0 ± 1.0 kcal mol–1 for ortho-, meta-, and para-benzyne, respectively (1 kcal mol–1 = 4.184 kJ mol–1). Whereas the paper predominantly focuses on the experimentally determined values, it also provides a comparison with theoretical studies that have examined the absolute thermochemical properties of the benzynes.