Enthalpy of Formation of Carbocycles: A Precise Theoretical Determination of Experimentally Imprecise Measurements.

Abstract

Despite being one of the best-known families of organic compounds, the fact that hydrocarbons exhibit a rich variety of structures owing to branching, cyclization, and the presence of multiple bonds, means that many of their properties are yet to be determined accurately, or even at all. Among cyclic hydrocarbons, those with three-membered rings are particularly interesting because of their strain energy. In this paper, we report accurate calculations of the enthalpy of formation of three-membered carbocycles, whose experimental values have not been obtained by direct measurement of the heat of combustion. For this purpose, we used several accurate composite methods to obtain the gas-phase enthalpies of atomization and derived from them the gas-phase enthalpies of formation, using experimentally determined accurate values for the atoms. Moreover, to minimize the inaccuracy that can possibly arise in this procedure, we also used homodesmotic reactions designed to balance systematic errors in the geometric and electronic structure of some of the species. A careful analysis of the results shows that some of the indirectly derived values reported in the literature are far from the most accurate theoretical outcomes, and we suggest that these new ones should be adopted.