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Homo‐ and Heteroleptic Coordination Polymers and Oxido Clusters of Bismuth(III) Vinylsulfonates
Author(s) -
Wrobel Lydia,
Rüffer Tobias,
Korb Marcus,
Krautscheid Harald,
Meyer Jens,
Andrews Philip C.,
Lang Heinrich,
Mehring Michael
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201803664
Subject(s) - homoleptic , chemistry , bismuth , acetonitrile , coordination polymer , solvent , medicinal chemistry , phosphonate , polymer , polymer chemistry , stereochemistry , crystallography , inorganic chemistry , metal , organic chemistry
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 BiPh 3 and vinylsulfonic acid in ethanol produces [{Ph 2 Bi(O 3 SCH=CH 2 )} 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(O 3 SCH=CH 2 ) 2 } n ] ( 2 ) and BiPh 3 . Compound 2 is obtained as a single product by the reaction of BiPh 3 with vinylsulfonic acid in acetonitrile and crystallizes as a one‐dimensional coordination polymer. The homoleptic vinylsulfonate [{Bi(O 3 SCH=CH 2 ) 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 [Bi 6 O 4 (OH) 4 (NO 3 ) 6 ]⋅H 2 O or [Bi 38 O 45 (OMc) 24 (dmso) 9 (H 2 O) 2 ]⋅2 DMSO⋅5 H 2 O (OMc=methacrylate) with vinylsulfonic acid, such a cluster, namely, [Bi 9 O 7 (OH)(O 3 SCH=CH 2 ) 11 (dmso) 11 ](O 3 SCH=CH 2 )⋅3 DMSO ( 4 ), is available as the main product. Starting from the hexanuclear bismuth oxido nitrate, another cluster, [Bi 38 O 45 (NO 3 ) 8 (O 3 SCH=CH 2 ) 14 (dmso) 18 ](O 3 SCH=CH 2 ) 2 ⋅2 DMSO ( 5 ), was observed as a co‐crystallizing side product, which upon further hydrolysis afforded [Bi 38 O 45 (NO 3 ) 6 (OH) 4 (O 3 SCH=CH 2 ) 12 (dmso) 23 (H 2 O) 2 ](O 3 SCH=CH 2 ) 2 ⋅2 H 2 O ( 6 ).