Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 2009-04-16

2- and 3-acetylpyrroles: a combined calorimetric and computational study.

Ana Filipa L O M Santos, José R B Gomes, Manuel A V Ribeiro da Silva

Index: J. Phys. Chem. A 113(15) , 3630-8, (2009)

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Abstract

A combined experimental and computational study on the thermochemistry of 2- and 3-acetylpyrroles was performed. The enthalpies of combustion and sublimation were measured by static bomb combustion calorimetry and Knudsen effusion mass-loss technique, respectively, and the standard (p(o) = 0.1 MPa) molar enthalpies of formation, in the gaseous phase, at T = 298.15 K, were determined. Additionally, the gas-phase enthalpies of formation were estimated by G3(MP2)//B3LYP calculations, using several gas-phase working reactions, and were compared with the experimental ones. N-H bond dissociation enthalpies, gas-phase acidities and basicities, proton and electron affinities and ionization enthalpies were also calculated. Experimental and theoretical results are in good agreement and show that 2-acetylpyrrole is thermodynamically more stable than the 3-isomer. The substituent effects of the acetyl group in pyrrole, thiophene and pyridine rings were also analyzed.