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

摘要

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 dimensional