South African Journal of Chemistry
versão On-line ISSN 1996-840X
MUZOMWE, Mayaliwa; BOECKX, Bram; MAES, Guido e KASENDE, Okuma E.. Discrimination between O-H...N and O-H...O=C complexes of 3-methyl-4-pyrimidone and methanol. A matrix-isolation FT-IR and theoretical DFT/B3LYP investigation. S.Afr.j.chem. (Online) [online]. 2011, vol.64, pp. 23-33. ISSN 1996-840X.
FT-IR matrix-isolated spectra for 3-methyl-4-pyrimidone and its H-bonded complexes with methanol in Ar were studied with the aim of discriminating between O-H...N and O-H...O=C complexes. Theoretical calculations were carried out using the DFT/B3LYP/6-31 + G(d) methodology in an attempt to predict the preferred interaction site of the 3-methyl-4-pyrimidone molecule with proton donors. The observed frequency decrease of the v(C=O) mode of 3-methyl-4-pyrimidone and the appearance of a broad v(OH...O) band in the spectrum of the complex with methanol suggest that H-bonding with methanol occurs at the carbonyl group. Computed binding energies of the hydrogen-bonded complexes (ΔEc) and computed intermolecular distances (r(O...H)) confirm that the O-H...O=C complex is preferred with methanol. However, for H-bonding with stronger acids such as HCl, the computational data suggest that the H-bonding occurs at the N1 ring atom of 3-methyl-4-pyrimidone.
Palavras-chave : Matrix-isolation; 3-methyl-4-pyrimidone; methanol; FT-IR spectroscopy; DFT/B3LYP calculations.