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

AuthorsBarreiro, Elena; Casas, José S.; Couce, María D.; Laguna, Antonio ; López-de-Luzuriaga, José M.; Monge, Miguel; Sánchez, Agustin; Sordo, José; Vázquez-López, Ezequiel M.
Issue Date2013
PublisherRoyal Society of Chemistry (UK)
CitationDalton Transactions 42(16): 5916-5923 (2013)
AbstractThe 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.
Identifiersdoi: 10.1039/C3DT33003F
issn: 1477-9226
e-issn: 1477-9234
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