title: A novel hexanuclear silver(I) cluster containing a regular Ag6 ring with short Ag-Ag distances and an argentophilic interaction.
abstract: 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.
authors: Departamento de Química Inorgánica, Facultade de Farmacia, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain.
authors: Elena
authors: E
authors: Barreiro
authors: José S
authors: JS
authors: Casas
authors: María D
authors: MD
authors: Couce
authors: Antonio
authors: A
authors: Laguna
authors: José M
authors: JM
authors: López-de-Luzuriaga
authors: Miguel
authors: M
authors: Monge
authors: Agustin
authors: A
authors: Sánchez
authors: José
authors: J
authors: Sordo
authors: Ezequiel M
authors: EM
authors: Vázquez López
mesh_terms: D000838:Anions / Q000737:chemistry; D056831:Coordination Complexes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006860:Hydrogen Bonding; D008958:Models, Molecular; D008968:Molecular Conformation; D011437:Propylamines / Q000737:chemistry; D012834:Silver / Q000737:chemistry*
chemical_list: D000838:Anions; D056831:Coordination Complexes; D011437:Propylamines; D012834:Silver; C007442:diisopropylamine