Theoretical studies on an unusual [Ag]+⋯ [Au]-⋯ [Au]-⋯ [Ag]+ metallophilic pattern: Dispersive forces vs. classical coulomb forces

  1. Donamaría, R. 1
  2. Lippolis, V. 2
  3. López-de-Luzuriaga, J.M. 1
  4. Monge, M. 1
  5. Elena Olmos, M. 1
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 University of Cagliari
    info

    University of Cagliari

    Cagliari, Italia

    ROR https://ror.org/003109y17

Revista:
Computational and Theoretical Chemistry

ISSN: 2210-271X

Any de publicació: 2014

Volum: 1030

Pàgines: 53-58

Tipus: Article

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DOI: 10.1016/J.COMPTC.2013.12.017 SCOPUS: 2-s2.0-84893004734 WoS: WOS:000332431400008 GOOGLE SCHOLAR

Altres publicacions en: Computational and Theoretical Chemistry

Objectius de Desenvolupament Sostenible

Resum

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.