Co<sub>2</sub>(CO)<sub>6</sub>(μ,η<sup>2</sup>-HCCFc) as Precursor in the Synthesis of Multiredox Cyclic and Linear Vinylferrocenylsiloxanes
作者:Covadonga Blasco、Sonia Bruña、Isabel Cuadrado、Esther Delgado、Elisa Hernández
DOI:10.1021/om201018h
日期:2012.4.9
Novel vinylferrocenyl-functionalized cyclic and linear polysiloxanes [MeSiC(Fc)=CH2}O](4) (1) and (Me3SiO)-(MeSiC(Fc)=CH2}O)(n) (SiMe3) (n approximate to 35) (3) (Fc = (eta(5)-C5H4)Fe(eta(5)-C6H6) have been synthesized by hydrosilylation reactions of the heterometallic compound Co-2(CO)(6)(mu,eta(2)-HCCFc) with the Si-H-functionalized polysiloxane frameworks [MeSiHO](4) and (Me3SiO)(MeSiHO) (SiMe3). The solution electrochemical behavior of polysiloxanes 1 and 3 has been investigated and showed that all the vinylferrocenyl units present in the molecules are electrochemically independent. Both neutral tetrametallic cyclotetrasiloxane 1 and,polysiloxane 3 become insoluble upon complete oxidation to the corresponding polycationic species, yielding electroactive films on platinum electrodes. In addition, stable electrode surfaces modified with the polyvinylferrocenylsiloxane 3 have been prepared and electrochemically characterized. The well-defined and persistent redox waves of electrodes coated with the polyvinylferrocenylsiloxane films are Characteristic of electrochemically stable, surface-confined reversible redox couples.