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.
Anufriev, S.A., Erokhina, S.A., Suponitsky, K.Y., Anisimov, A.A., Laskova, J.N., Godovikov, I.A., et al. (2018). Synthesis and structure of bis(methylsulfanyl) derivatives of iron bis(dicarbollide). JOURNAL OF ORGANOMETALLIC CHEMISTRY, 865, 239-246 [10.1016/j.jorganchem.2018.04.019].
Synthesis and structure of bis(methylsulfanyl) derivatives of iron bis(dicarbollide)
Fabrizi de Biani, Fabrizia;Corsini, Maddalena;
2018-01-01
Abstract
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.File | Dimensione | Formato | |
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https://hdl.handle.net/11365/1072904