The Synthesis,Structure And Electrochemical Characteristics Of Ferrocene Derivatives

Since its discovery, ferrocene and its derivatives play an important role in organometallic chemistry due to their potential use in catalysis, material science, molecular devices, hydrometallurgy, and electrochemistry. Of particular interest are the properties of the redox of the iron center and the sandwich structures. However, we were surprised that there has been limited study of their electrochemistry character and the kinetic parameters. In this thesis, we have done some work and the main results are expressed as follows:1. Two novel ferrocene derivatives FcL1 [N-(2-hydroxybenzylidene) -3-ferrocenylaniline] and FcL2 [N- (2-hydroxybenzylidene)-4-ferrocenylaniline] were synthesized by the reaction of 3-fer-rocenylaniline or 4-ferrocenylaniline and salicylal. The compounds were determined by elemental analysis, IR, UV and 2HNMR spectrometer, respectively. Electrochemical studies reveal that properties of FcL1 were very similar with that of FcL2, which the electron withdrawing imine group substantially influences the redox potential of the iron center and oxidation of the substituents on the ferrocene moiety leads to an electrode passivation process. Moreover, their diffusion coefficient (D) and standard rate constant of the electrode reaction (ks) were also obtained, and the effect of substituents on the kinetic parameters was discussed.2. Reactions of formylferrocene and 1, 2-di- (o-aminophenoxy) ethane yield the novel bis (ferrocenyl) receptor (FcL3). This compound has also been characterized by IR, 'HNMR and elemental analysis. The X-ray crystal structure of FcL3 was described. In addition, the electrochemical behavior of FcL/3 was investigated in detail in 0.1M tetra-n-butylammonium perchlorate (TBAP) + CH3CN by cyclic voltammetry (CV) and chronoamperometry. Its coordination properties with metal ions in acetonitrile were also studied. The FcL3 show a two-wave behavior for Cu2+, Zn2+ and Ni2+, but was unresponsive to Mg2+ and Ca2+. The maximum oxidation peak potential shift of about 250mV was found for FcL in the presence of Cu2+, Zn2+ or Ni2+. These may provide some useful information related to the potential application of this novel complexion.3. Two novel bis ferrocene thiourea derivatives FcL4 [N-(3-ferrocenylphenyl)-N'-4- (ferroc-enylbencarboxyl) thiourea] and FcL5 [N-(4-ferrocenylphenyl)-N'-4- (ferrocenylbencarboxyl) thiourea] were synthesized. The compounds were determined by IR, 1HNMR spectrometer and electrochemical analysis, respectively. It was found that the electrochemical property of FcL4 was very similar with FcL5, the redox couple was corresponding to the progress of 2Fc3++2e-(?) 2Fc2+, which can be rationalized by the equivalent environment of the ferrocene subunit in each case. In addition, the different electrochemical character of different substituents, m-ferrocenylaniline and p-ferrocenylaniline, were discussed and the electrode reaction mechanism of FcL5 were also obtained.