Triphenylbismuth(v) di[(iso)nicotinates] - transmetallation agents or divergent organometalloligands? First organobismuth(v)-based silver(i) coordination polymers.

The reaction of Ph3BiCl2 with alkali salts of isonicotinic and nicotinic acids afforded Ph3Bi[O(O) CC5H4N-4](2) (1) and Ph3Bi[O(O) CC5H4N-3](2) (2), respectively, which were characterized by multinuclear NMR spectroscopy in solution, mass spectrometry and IR spectroscopy in the solid state. Their molecular structures were established by single-crystal X-ray diffraction. For both 1 and 2 the molecules contain a trigonal bipyramidal C3BiO2 core, with the phenyl groups in equatorial positions. The potential use of 1 and 2 as ditopic organometalloligands was investigated. The reaction of 1 or 2 with Me3SnCl (1 : 2 molar ratio) resulted in carboxylato ligand exchange and the formation of Me3Sn[O(O)CC5H4N-4] (3) and Me3Sn [O(O) CC5H4N-3] (4) besides Ph3BiCl2. The crystals of both 3 and 4 contain 1-D coordination polymers built through intermolecular N -> Sn interactions. The treatment of Ni[S2P((OPr)-Pr-i)(2)](2) with 1 and 2, respectively, resulted, in addition to di(carboxylato) nickel(II) derivatives, in isolation of Ph3Bi and the disulphane [(iPrO)(2)P(S)S](2). New coordination polymers were obtained by reacting 1 and 2 with various silver(I) salts: [Ag{Ph3Bi[O(O)CC5H4N-4](2)}(OTf)] (5), [Ag{Ph3Bi[O(O)CC5H4N-3](2)}(OTf)]center dot CH2Cl2 (6 center dot CH2Cl2), [Ag{Ph3Bi[O(O) CC5H4N-4](2)}](SbF6)center dot 2THF(7 center dot 2THF),[Ag{Ph3Bi[O(O)CC5H4N-3](2)}](SbF6)center dot CH2Cl2 (8 center dot CH2Cl2) and [Ag{Ph3Bi [O(O) CC5H4N-3](2)}(NO3)]center dot CH2Cl2 (9 center dot CH2Cl2). The crystal structures of 5 and 6 can be described as 1-D chains linked by triflate bridges in pairs of chains and 2-D networks, respectively. Compound 7 features a 2-D grid-like topology of the network, with tecton 1 acting as a tridentate ligand through both nitrogen and one oxygen atoms. The linker 2 molecules adopt either cis (compound 6) or trans (compounds 8 and 9) conformation. Complexes 8 and 9 are 1-D chain polymers exhibiting zig-zag and wavy motifs, respectively. The dimensionality of the structures is extended by the presence of supramolecular interactions (pi center dot center dot center dot pi, Ag center dot center dot center dot Ag, Ag center dot center dot center dot O).