The role of aromatic interactions in the structure and energetics of benzyl ketones

• Tipo: Artigo em Revista Científica Internacional
• Data: 2010

Autores

Carlos F. R. A. Lima (Autor) FCUP; Carlos A. D. Sousa (Autor) FCUP; José E. Rodríguez-Borges (Autor) FCUP; André Melo (Autor) FCUP; Ligia R. Gomes (Autor) FCUP; John N. Low (Autor) Outra; Luís M. N. B. F. Santos (Autor) FCUP

Revista

Título: Physical Chemistry Chemical Physics

Vol. 12 Nº 36

Páginas: 11228-11237

ISSN: 1463-9076

Editora: Royal Society of Chemistry

Indexação

ISI Web of Knowledge - 14 Citações

Scopus - 14 Citações

Classificação Científica

FOS: Ciências da engenharia e tecnologias > Engenharia química

Outras Informações

ID Authenticus: P-003-CA4

DOI: 10.1039/c003941a

Abstract (EN): A qualitative and quantitative energetic and structural study of dibenzyl ketone (DBK) and benzyl ethyl ketone (BEK) was carried out in order to obtain insights into the type and magnitude of aromatic interactions that these systems present in their different phases. The crystal structure of DBK was obtained by X-ray crystallography, and it shows that the conformation adopted in the crystalline state is governed by the intermolecular interactions. The standard (p(0) = 10(5) Pa) molar enthalpy of formation in the gaseous state at T = 298.15 K was derived by Calvet and combustion calorimetry. Using a homodesmic reaction scheme, the first calorimetric evaluation of the interaction enthalpy between two stacked phenyl rings is presented. A stabilizing enthalpic effect of (12.9 +/- 4.9) kJ mol(-1) associated with the intramolecular pi-pi interaction in DBK was found. The gas phase intramolecular pi ... pi interaction in DBK is in agreement with quantum chemical calculations at B3LYP/6-311++ G(d, p) and MP2 with various basis-sets. An intramolecular pi ... pi interaction in DBK and a weak C-H ... pi interaction in BEK were found by variable-temperature (1)H-NMR spectroscopy in MeOD. These observations are consistent with a hindered rotor interpretation, supported by ab initio calculations for the gas phase at the MP2/cc-pVDZ level. The global results indicate a distinct molecular structure on going from crystalline DBK to liquid, gas, and solution phases, ruled by the overall contribution of the intra- and intermolecular interactions.

Idioma: Inglês

Tipo (Avaliação Docente): Científica

Nº de páginas: 10