Syntheses, structures, and properties of the complexes [Ag(N ∧ S)n] (X), N ∧ S=1-methyl-2-(alkylthiomethyl)-1H-benzimidazoles, X = PF6 (n=2) or PO2F2 (n=1)

The complexes [Ag(eta(2)-N<^>S)(2)](PF6), N<^>S = 1-methyl-2-(methylthiomethyl)-1H-benzimidazole, mmb (complex 1) or 1-methyl-2-(tert-butylthiomethyl)-1H-benzimidazole, mtb (complex 2), and [Ag(mu,eta(2)-mmb)(eta,eta(2)-O2PF2)] (complex 3) were synthesized and characterized by X-ray crystallography. Long Ag-S (ca. 2.70 Angstrom) and shorter Ag-N bonds (ca. 2.23 Angstrom) are part of characteristically distorted tetrahedral coordination arrangements at the silver(I) ions in 1 and 2. Unexpectedly, the comparison with the copper analogue [Cu(eta(2)-mmb)(2)](PF6) reveals a more tetrahedral and less linear coordination arrangement for the corresponding silver species. Compound 3 as obtained by hydrolysis of the PF6 ion or by the use of AgPO2F2 exhibits bridging mmb and eta(2)-difluorophosphate ligands in a chain-type structure.