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

Abstract

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(OⁱPr)₂]₂ with 1 and 2, respectively, resulted, in addition to di(carboxylato)nickel(II) derivatives, in isolation of Ph₃Bi and the disulphane [(ⁱPrO)₂P(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)]·CH₂Cl₂ (6·CH₂Cl₂), [Ag{Ph₃Bi[O(O)CC₅H₄N-4]₂}](SbF₆)·2THF (7·2THF), [Ag{Ph₃Bi[O(O)CC₅H₄N-3]₂}](SbF₆)·CH₂Cl₂ (8·CH₂Cl₂) and [Ag{Ph₃Bi[O(O)CC₅H₄N-3]₂}(NO₃)]·CH₂Cl₂ (9·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 (π⋯π, Ag⋯Ag, Ag⋯O).