A novel hexanuclear silver(i) cluster containing a regular Ag6 ring with short Ag-Ag distances and an argentophilic interaction

  1. Barreiro, E. 2
  2. Casas, J.S. 2
  3. Couce, M.D. 3
  4. Laguna, A. 4
  5. López-De-Luzuriaga, J.M. 1
  6. Monge, M. 1
  7. Sánchez, A. 2
  8. Sordo, J. 2
  9. Vázquez López, E.M. 3
  1. 1 Universidad de La Rioja

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 Universidade de Santiago de Compostela

    Universidade de Santiago de Compostela

    Santiago de Compostela, España

    ROR https://ror.org/030eybx10

  3. 3 Universidade de Vigo

    Universidade de Vigo

    Vigo, España

    ROR https://ror.org/05rdf8595

  4. 4 Instituto de Nanociencia y Materiales de Aragón

    Instituto de Nanociencia y Materiales de Aragón

    Zaragoza, España

    ROR https://ror.org/031n2c920

Dalton Transactions

ISSN: 1477-9226

Datum der Publikation: 2013

Ausgabe: 42

Nummer: 16

Seiten: 5916-5923

Art: Artikel

DOI: 10.1039/C3DT33003F SCOPUS: 2-s2.0-84877028959 WoS: WOS:000316869400040 GOOGLE SCHOLAR

Andere Publikationen in: Dalton Transactions

Objetivos de desarrollo sostenible


The hexanuclear complex [HQ][Ag(p-mpspa)] (H2-p-mpspa = 3-(4-methoxyphenyl)-2-sulfanylpropenoic acid) was prepared by reacting the precursor [Ag(H-p-mpspa)] with diisopropylamine (Q). The complex was characterized by spectroscopic techniques and the structure was solved by a single crystal X-ray diffraction study. The crystal contains hydrogen-bonded diisopropylammonium cations and [Ag6(p-mpspa)6] 6- anions that are based on a regular Ag6 ring with each S-donor atom of the sulfanylcarboxylate ligand bridging two Ag atoms. The Ag-Ag bond distances, 2.8036(6) Å, are very short and suggest a closed shell d10⋯d10 argentophilic interaction. To analyze the relative role of this interaction and that of the S-bridging atom the anionic [Ag6(p-mpspa)6]6- moiety has been studied theoretically at the Hartree-Fock (HF) and 2nd order Møller-Plesset perturbation theory (MP2) levels on a very simple [Ag 6(SH)6] A model system. A large model system [Ag 6(p-mpspa)6]6-B has also been studied by applying the ONIOM (QM/MM) approach using HF/UFF and MP2/UFF combinations as levels of theory. The six experimentally observed Ag(i)⋯Ag(i) supported interactions are reproduced when dispersion-type interactions are considered in the theory levels MP2 and ONIOM MP2/UFF for models A and B, respectively. The use of HF and ONIOM HF/UFF levels led to a similar hexanuclear structure but displayed a large hexagonal disposition without argentophilic contacts for both models A and B. The steric hindrance exerted by the ligands did not preclude the formation of argentophilic interactions, as observed experimentally. © 2013 The Royal Society of Chemistry.