NDLI: A novel hexanuclear silver(I) cluster containing a regular $Ag_{6}$ ring with short Ag–Ag distances and an argentophilic interaction

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	López-de-luzuriaga, José M. Laguna, Antonio Monge, Miguel Casas, José S. Barreiro, Elena Couce, María D. Sordo, José Vázquez López, Ezequiel M. Sánchez, Agustin
Description	Author Affiliation: Barreiro E ( Departamento de Química Inorgánica, Facultade de Farmacia, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain.)
Abstract	The hexanuclear complex [HQ][Ag(p-mpspa)] $(H_{2}-p-mpspa$ = 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 $[Ag_{6}(p-mpspa)_{6}]^{6−}$ anions that are based on a regular $Ag_{6}$ 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 $[Ag_{6}(p-mpspa)_{6}]^{6−}$ moiety has been studied theoretically at the Hartree–Fock (HF) and $2^{nd}$ order Møller–Plesset perturbation theory (MP2) levels on a very simple $[Ag_{6}(SH)_{6}]$ 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.
ISSN	14779226
Issue Number	16
Volume Number	42
e-ISSN	13645447
Journal	Dalton Trans.
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2013-04-28
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Coordination Complexes Chemistry Silver Anions Crystallography, X-Ray Hydrogen Bonding Models, Molecular Molecular Conformation Propylamines Journal Article Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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