Syntheses and Reactions of Ferrocene-Containing Polymers, VI. Polarography and Electron Transfer Equilibria of Some Ferrocene-Containing Polymers

Abstract

Abstract Polarography and electron transfer equilibria of some ferrocene-containing polymers were studied in comparison with small-molecule analogs. The oxidation half-wave potentials of polyvinylferrocene and polydivinylferrocene (almost completely cyclized) in CH2Cl2 were close to those of ferrocene and [3]ferrocenophane, respectively. This is in line with structural similarity. Only one oxidation step was observed in the polarogram of triferrocenylbenzene and polyethynylferrocene, suggesting that the electronic interactions between ferrocene units are small in these compounds. Electron transfer equilibrium was observed between ferrocene units in polymer and iodine. Equilibrium constants of the [3]ferrocenophane unit were greater than those of the unbridged ferrocene unit. The ferrocene unit in polymer showed greater equilibrium constants than those of their small-molecule analogs.