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Published on: July 14, 2015
Homo- and Heteroleptic Coordination Polymers and Oxido Clusters of Bismuth(III) Vinylsulfonates
Lydia Wrobel1, Tobias Rüffer2, Marcus Korb2
1Fakultät für Naturwissenschaften, Institut für Chemie, Professur Koordinationschemie, Technische Universität Chemnitz, 09107, Chemnitz, Germany.
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 [{Ph2 Bi(O3 SCH=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(O3 SCH=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(O3 SCH=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 [Bi6 O4 (OH)4 (NO3 )6 ]⋅H2 O or [Bi38 O45 (OMc)24 (dmso)9 (H2 O)2 ]⋅2 DMSO⋅5 H2 O (OMc=methacrylate) with vinylsulfonic acid, such a cluster, namely, [Bi9 O7 (OH)(O3 SCH=CH2 )11 (dmso)11 ](O3 SCH=CH2 )⋅3 DMSO (4), is available as the main product. Starting from the hexanuclear bismuth oxido nitrate, another cluster, [Bi38 O45 (NO3 )8 (O3 SCH=CH2 )14 (dmso)18 ](O3 SCH=CH2 )2 ⋅2 DMSO (5), was observed as a co-crystallizing side product, which upon further hydrolysis afforded [Bi38 O45 (NO3 )6 (OH)4 (O3 SCH=CH2 )12 (dmso)23 (H2 O)2 ](O3 SCH=CH2 )2 ⋅2 H2 O (6).
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