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 [Ag 2 (μ‐O 2 CCF 3 ) 2 (μ‐dppf)] ( 1 ) and [Ag 2 (η 1 ‐O 2 CCF 3 ) 2 (dppf) 2 ] ( 2 ). Treatment of 1 with excess dppf gave a coordination polymeric compound [Ag(η 2 ‐O 2 CCF 3 )(dppf)] n ( 3 ). Reaction of 1 with PMe 2 Ph in MeOH in the presence of NH 4 PF 6 led to displacement of trifluoroacetate, forming the mononuclear compound [Ag(PMe 2 Ph) 2 (η 2 ‐dppf)]PF 6 ( 4 ). All compounds have been characterized by microanalytical and spectroscopic analyses [IR, MS and NMR ( 1 H, 19 F and 31 P{ 1 H})] as well as X‐ray diffraction studies. Molecular structures of the solvates of 1 , viz. 1A ( 1· 0.5THF) and 1B ( 1· 0.5CH 2 Cl 2 ), 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)