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Issue 16, 2013
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A novel hexanuclear silver(I) cluster containing a regular Ag6 ring with short Ag–Ag distances and an argentophilic interaction

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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 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 [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.

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

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Publication details

The article was received on 14 Dec 2012, accepted on 08 Feb 2013 and first published on 11 Feb 2013


Article type: Paper
DOI: 10.1039/C3DT33003F
Citation: Dalton Trans., 2013,42, 5916-5923
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    A novel hexanuclear silver(I) cluster containing a regular Ag6 ring with short Ag–Ag distances and an argentophilic interaction

    E. Barreiro, J. S. Casas, M. D. Couce, A. Laguna, J. M. López-de-Luzuriaga, M. Monge, A. Sánchez, J. Sordo and E. M. Vázquez López, Dalton Trans., 2013, 42, 5916
    DOI: 10.1039/C3DT33003F

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