Synthesis and structure of Bis(Methylsulfanyl) derivatives of iron Bis(Dicarbollide)статья
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Аннотация:Bis(methylsulfanyl) derivatives of iron(II) bis(dicarbollide) [8,8'-(MeS)2-3,3'-Fe(1,2-C2B9H10)2]2- (42-),[4,4'-(MeS)2-3,3'-Fe(1,2-C2B9H10)2]2- (52-), and [4,7'-(MeS)2-3,3'-Fe(1,2-C2B9H10)2]2- (62-) were prepared by the treatment of the corresponding dimethylsulfonium derivatives 1-3 with potassium butylthiolate. Their oxidation by air in aqueous solution results in the corresponding derivatives of iron(III) bis(dicarbollide)[8,8'-(MeS)2-3,3'-Fe(1,2-C2B9H10)2]- (7-), [4,4'-(MeS)2-3,3'-Fe(1,2-C2B9H10)2]- (8-) and [4,7'-(MeS)2-3,3'-Fe(1,2-C2B9H10)2]- (9-). The structures of (Bu4N)2[8,8'-(MeS)2-3,3'-Fe(1,2-C2B9H10)2] and (Me4N)[4,7'-(MeS)2-3,3'-Fe(1,2-C2B9H10)2] were determined through single-crystal X-ray diffraction. In the solid state, the rotation of the dicarbollide ligands with respect to each other is hampered due to formation of weak intramolecular CH⋯S(Me) hydrogen bonds between the ligands resulting in stabilization of transoid-conformation in the case of 8,8'-isomer and gauche-conformation in the case of 4,4'- and 4,7'-isomers. The synthesized bis(methylsulfanyl) derivatives of iron bis(dicarbollide) can be considered as a versatile platform for design of molecular switches.