Metal imidazolato polymers: synthesis, characterization and crystal structure of new silver(I) triphenylphosphine derivatives

When the polymeric complex [Ag(im)]n (Him = imidazole) is reacted with PPh3 (PPh3 = triphenylphosphine), it yields the [Ag2(mu2-im)2(PPh3)3] and [Ag(mu2-im)(PPh3)2]n species, shown to contain wavy chains of metal ions, singly bridged by N,N'-exobidentate imidazolate ligands. The former, crystallised as the CH2Cl2 solvate, contains two non-equivalent silver(I) ions, differing in the number of coordinated phosphines (one, in trigonal planar stereochemistry, or two, having tetrahedral geometry). The latter has a unique independent silver(I) ion in a tetrahedral environment, with two coordinated PPh3 ligands. The reactivity of known silver(I) azolates with PPh3, as well as the solution behaviour and (when available) the crystal structures of the corresponding derivatives are taken into consideration for a due comparison.