Energetics and molecular structure of 2,5-dimethyl-1-phenylpyrrole and 2,5-dimethyl-1-(4-nitrophenyl)pyrrole.
Thermochemical and thermodynamic properties of 2,5-dimethyl-1-phenylpyrrole and 2,5-dimethyl-1-(4-nitrophenyl)pyrrole have been determined by using a combination of calorimetric and effusion techniques as well as high-level ab initio molecular orbital calculations. The standard (p° = 0.1 MPa) molar enthalpies of formation, in the crystalline state, Δ(f)H(m)°(cr), at T = 298.15 K, were derived from the standard molar enthalpies of combustion, Δ(c)H(m)°, which were obtained from static bomb combustion calorimetry. The Knudsen mass-loss effusion technique was used to determine the standard molar enthalpies of sublimation, Δ(cr)(g)H(m)°, at T = 298.15 K. From the experimental results, the standard molar enthalpies of formation, in the gaseous phase, at T = 298.15 K, were derived. The results were analyzed and interpreted in terms of enthalpic increments and molecular structure. For comparison purposes, standard ab initio molecular calculations at the G3(MP2)//B3LYP level were performed, using a set of working reactions and the gas-phase enthalpies of formation of both compounds were estimated; the results are in excellent agreement with experimental data. The computational study was also extended to the determination of proton and electron affinities, basicities and adiabatic ionization enthalpies.
da Silva
Manuel A V Ribeiro
MA
Centro de Investigação em Química, Department of Chemistry, Faculty of Science, University of Porto, Rua do Campo Alegre, 687, P-4169-007 Porto, Portugal. risilva@fc.up.pt
Santos
Ana Filipa L O M
AF