Homo- and Heteroleptic Coordination Polymers and Oxido Clusters of Bismuth(III) Vinylsulfonates
Dedicated to Professor Dietmar Stalke on the occasion of his 60th birthday
Abstract
The synthesis and characterization of six homo- and heteroleptic coordination polymers and oxido clusters of bismuth(III) vinylsulfonates are reported. The solvent-mediated reaction of BiPh3 and vinylsulfonic acid in ethanol produces [{Ph2Bi(O3SCH=CH2)}n] (1), which crystallizes as a one-dimensional coordination polymer as a result of bridging sulfonato ligands accompanied by intermolecular Bi⋅⋅⋅ π(arene) London dispersion interactions. In solution, compound 1 equilibrates to give [{PhBi(O3SCH=CH2)2}n] (2) and BiPh3. Compound 2 is obtained as a single product by the reaction of BiPh3 with vinylsulfonic acid in acetonitrile and crystallizes as a one-dimensional coordination polymer. The homoleptic vinylsulfonate [{Bi(O3SCH=CH2)3}n] (3) was isolated as a two-dimensional coordination polymer, which is quite moisture sensitive, but did not provide a distinct polynuclear bismuth oxido cluster upon hydrolysis. However, by treatment of [Bi6O4(OH)4(NO3)6]⋅H2O or [Bi38O45(OMc)24(dmso)9(H2O)2]⋅2 DMSO⋅5 H2O (OMc=methacrylate) with vinylsulfonic acid, such a cluster, namely, [Bi9O7(OH)(O3SCH=CH2)11(dmso)11](O3SCH=CH2)⋅3 DMSO (4), is available as the main product. Starting from the hexanuclear bismuth oxido nitrate, another cluster, [Bi38O45(NO3)8(O3SCH=CH2)14(dmso)18](O3SCH=CH2)2⋅2 DMSO (5), was observed as a co-crystallizing side product, which upon further hydrolysis afforded [Bi38O45(NO3)6(OH)4(O3SCH=CH2)12(dmso)23(H2O)2](O3SCH=CH2)2⋅2 H2O (6).
