Fakultät für Naturwissenschaften, Institut für Chemie, Professur Koordinationschemie, Technische Universität Chemnitz, 09107, Chemnitz, Germany.
Fakultät für Naturwissenschaften, Institut für Chemie, Professur Anorganische Chemie, Technische Universität Chemnitz, 09107, Chemnitz, Germany.
Chemistry. 2018 Nov 7;24(62):16630-16644. doi: 10.1002/chem.201803664. Epub 2018 Oct 17.
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 BiPh and vinylsulfonic acid in ethanol produces [{Ph Bi(O SCH=CH )} ] (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(O SCH=CH ) } ] (2) and BiPh . Compound 2 is obtained as a single product by the reaction of BiPh with vinylsulfonic acid in acetonitrile and crystallizes as a one-dimensional coordination polymer. The homoleptic vinylsulfonate [{Bi(O SCH=CH ) } ] (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 [Bi O (OH) (NO ) ]⋅H O or [Bi O (OMc) (dmso) (H O) ]⋅2 DMSO⋅5 H O (OMc=methacrylate) with vinylsulfonic acid, such a cluster, namely, [Bi O (OH)(O SCH=CH ) (dmso) ](O SCH=CH )⋅3 DMSO (4), is available as the main product. Starting from the hexanuclear bismuth oxido nitrate, another cluster, [Bi O (NO ) (O SCH=CH ) (dmso) ](O SCH=CH ) ⋅2 DMSO (5), was observed as a co-crystallizing side product, which upon further hydrolysis afforded [Bi O (NO ) (OH) (O SCH=CH ) (dmso) (H O) ](O SCH=CH ) ⋅2 H O (6).
报告了六种均配和杂配的铋(III)乙烯砜配位聚合物和氧化簇的合成与表征。在乙醇中，PhBi 和乙烯砜酸的溶剂介导反应生成 [{Ph Bi(O SCH=CH )} ]（1），由于桥连的磺酸盐配体伴随着分子间的 Bi⋅⋅⋅π（芳基）伦敦色散相互作用，该化合物结晶为一维配位聚合物。在溶液中，化合物 1 通过平衡得到 [{PhBi(O SCH=CH ) } ]（2）和 BiPh。化合物 2 通过 BiPh 与乙烯砜酸在乙腈中的反应得到单一产物，结晶为一维配位聚合物。均配的乙烯砜 [{Bi(O SCH=CH ) } ]（3）作为二维配位聚合物被分离出来，它对水分非常敏感，但水解后没有提供明显的多核铋氧化簇。然而，通过处理 [Bi O (OH) (NO ) ]⋅H O 或 [Bi O (OMc) (dmso) (H O) ]⋅2 DMSO⋅5 H O（OMc=甲基丙烯酸酯）与乙烯砜酸，得到了一种这样的簇，即 [Bi O (OH)(O SCH=CH ) (dmso) ](O SCH=CH )⋅3 DMSO（4），作为主要产物。从六核铋氧化硝酸盐出发，另一种簇 [Bi O (NO ) (O SCH=CH ) (dmso) ](O SCH=CH ) ⋅2 DMSO（5）作为共结晶的副产物被观察到，进一步水解得到 [Bi O (NO ) (OH) (O SCH=CH ) (dmso) (H O) ](O SCH=CH ) ⋅2 H O（6）。
