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

• Published in: Dalton transactions : an international journal of inorganic chemistry 2013-04, Vol.42 (16), p.5916-5923
• Main Authors: Barreiro, Elena, Casas, José S, Couce, María D, Laguna, Antonio, López-de-Luzuriaga, José M, Monge, Miguel, Sánchez, Agustin, Sordo, José, Vázquez López, Ezequiel M
• Format: Article
• Language: English
• Subjects: Anions - chemistry; Coordination Complexes - chemistry; Crystallography, X-Ray; Hydrogen Bonding; Models, Molecular; Molecular Conformation; Propylamines - chemistry; Silver - chemistry
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c3dt33003f

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 d(10)···d(10) 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 2(nd) order Møller-Plesset perturbation theory (MP2) levels on a very simple [Ag6(SH)6] A model system. A large model system [Ag6(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.