Vinyl-Functionalized Silanes and Disiloxanes with Electronically Communicated Ferrocenyl Units
A new series of vinyl-functionalized polyferrocenyl organosilicon compounds, including triferrocenylvinylsilane, (CH2CH)Si(Fc)3 (7) (Fc = (η5-C5H4)Fe(η5-C5H5)), 1,3-divinyl-1,1,3,3-tetraferrocenyldisiloxane, [(CH2CH)(Fc)2Si]2O (8), and 1,3-divinyl-1,3-dimethyl-1,3-diferrocenyldisiloxane, [(CH2CH)...
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Published in | Organometallics Vol. 29; no. 12; pp. 2796 - 2807 |
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Main Authors | , , , , |
Format | Journal Article |
Language | English |
Published |
WASHINGTON
American Chemical Society
28.06.2010
Amer Chemical Soc |
Subjects | |
Online Access | Get full text |
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Summary: | A new series of vinyl-functionalized polyferrocenyl organosilicon compounds, including triferrocenylvinylsilane, (CH2CH)Si(Fc)3 (7) (Fc = (η5-C5H4)Fe(η5-C5H5)), 1,3-divinyl-1,1,3,3-tetraferrocenyldisiloxane, [(CH2CH)(Fc)2Si]2O (8), and 1,3-divinyl-1,3-dimethyl-1,3-diferrocenyldisiloxane, [(CH2CH)(Fc)MeSi]2O (9), have been synthesized via the low-temperature salt metathesis reaction of monolithioferrocene and the chlorosilanes (CH2CH)SiCl3 and [(CH2CH)(Cl)MeSi]2O. Compounds 7−9 were characterized by elemental analysis, multinuclear (1H, 13C, 29Si) NMR spectroscopy, and MALDI-TOF mass spectrometry. The molecular structures of the vinyl-functionalized silane 7 and divinyldisiloxanes 8 and 9 in the solid state have been determined by single-crystal X-ray analysis. Whereas tetraferrocenyl compound 8 possesses a linear disiloxane skeleton (Si−O−Si bond angle of 180.0(2)°), biferrocenyl 9 shows a bent arrangement of the disiloxane linkage (Si−O−Si angle of 143.2(2)°). The oxidation electrochemical behavior of polyferrocenyl molecules 7−9 has been examined by cyclic voltammetry and square wave voltammetry in dichloromethane solution, using hexafluorophosfate, [PF6]−, and tetrakis(pentafluorophenyl)borate, [B(C6F5)4]−, as supporting electrolyte anions of different coordinating ability. Compound 7 can be reversibly oxidized in three consecutive steps to the trication 7 3+ . Divinyldisiloxanes 8 and 9 are reversibly oxidized in four and two one-electron-transfer steps, respectively, which suggests significant electronic interaction among the ferrocenyl redox centers linked by the short three-atom Si−O−Si bridge. |
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ISSN: | 0276-7333 1520-6041 |
DOI: | 10.1021/om1002733 |