Theoretical studies on an unusual [Ag]+⋯ [Au]-⋯ [Au]-⋯ [Ag]+ metallophilic pattern: Dispersive forces vs. classical coulomb forces
- Donamaría, R. 1
- Lippolis, V. 2
- López-de-Luzuriaga, J.M. 1
- Monge, M. 1
- Elena Olmos, M. 1
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1
Universidad de La Rioja
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2
University of Cagliari
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ISSN: 2210-271X
Año de publicación: 2014
Volumen: 1030
Páginas: 53-58
Tipo: Artículo
beta Ver similares en nube de resultadosOtras publicaciones en: Computational and Theoretical Chemistry
Resumen
We have studied theoretically the organometallic compound [{Au(C6Cl5)2}Ag([9]aneS3)]2, which displays an unprecedented [Ag]+-[Au]--[Au]--[Ag]+ sequence of metals, formed by unsupported Au(I)⋯ Au(I) and Au(I)⋯ Ag(I) interactions and weaker Cipso⋯ Ag and C6Cl5⋯ C6Cl5 π-stacking interactions. Density Functional Theory calculations using the pbe functional (DFT/pbe), Hartree-Fock (HF), and second-order Møller Plesset perturbation theory (MP2) calculations have been performed on five model systems based on the X-ray structure. Two dinuclear models (A1 and A2) have been used to estimate the BSSE-corrected interaction energy at HF and MP2 levels between one Ag(I) and one Au(I) fragment and permit to separate the Cipso⋯ Ag(I) and Au(I)⋯ Ag(I) contribution to the interaction. Three tetranuclear models (B1-B3) have been used to determine the Cipso⋯ Ag(I), Au(I)⋯ Ag(I), Au(I)⋯ Au(I) and π-stacking interactions present in the molecule. The HF level accounts for the ionic component of the interactions and the MP2 level also account for the dispersive contribution; both permits to study the nature and strength of all different types of interactions present in the molecule. © 2013 Elsevier B.V.