Supramolecular Structures in [Ag(dppf)] Complexes [dppf = 1,1′-Bis(diphenylphosphanyl)ferrocene] Stabilized by Coordinatively Versatile Trifluoroacetate (TFA) Ligands

The interaction of silver(I) trifluoroacetate and dppf in different molar equivalents has led to the isolation of dinuclear complexes [Ag2(μ‐O2CCF3)2(μ‐dppf)] (1) and [Ag2(η1‐O2CCF3)2(dppf)2] (2). Treatment of 1 with excess dppf gave a coordination polymeric compound [Ag(η2‐O2CCF3)(dppf)]n (3). Reaction of 1 with PMe2Ph in MeOH in the presence of NH4PF6 led to displacement of trifluoroacetate, forming the mononuclear compound [Ag(PMe2Ph)2(η2‐dppf)]PF6 (4). All compounds have been characterized by microanalytical and spectroscopic analyses [IR, MS and NMR (1H, 19F and 31P{1H})] as well as X‐ray diffraction studies. Molecular structures of the solvates of 1, viz. 1A (1·0.5THF) and 1B (1·0.5CH2Cl2), 2 and 3 show that they contain trifluoroacetate in bridging, monodentate and bidentate bonding modes, respectively, with dppf as a bridging co‐ligand. Compound 3 is an infinite linear [−dppf−Ag−dppf−Ag−dppf−Ag−]n coordination polymer. Interestingly, 1A and 1B form two different supramolecular network structures through C−H···F and C−H···O hydrogen‐bonding interactions. Such secondary bonding interactions also lead to the formation of a 3D supramolecular structure in 3. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)