Studies On The Syntheses,Properties Of Ferrocene-functionalized Polyamines And Chiral Cyclopalladated Ferrocenylimines

In this thesis, a novel ferrocenephane was synthesized. The coordinatibive properties towards Mg2+, Ni2+, Cu2+, Zn2+, Cd2+, Pb2+ have been investigated by a combination of cycle voltammetry. Two novel chiral ferrocenylimines were synthesized and their cyclopalladatation were studied. Among the compounds synthesized two single crystals were obtained, their structures and conformations were characterized. The main results obtained were as follows.1 Three ferrocene derivatives L1-L3 were designed and synthesized, andcharacterized by elemental analysis, IR, and NMR. L2 and L3 have been obtained by others, which were synthesized just for the aim of comparation with with L1. Electrochemical investigations have demonstrated that the binding of Mg2+, Ni2+, Cu2+, Zn2+, Cd2+, and Pb2+ by L1-L3 results in anodical shifts of the ferrocene-ferrocenium redox couple. In additional, it can be concluded as follows: L1 forms mono-nuclear complexes with these metal ions; L2 forms mono-nuclear complexes with Cd2+, Ni2+ and dinuclearcomplexes with Mg2+, Cu2*, Zn2+, Pb2*; L3 forms mono-nuclear complexes with Ni2+, Zn2+, Cd2+, Pb2+ except for Cu2+ and Mg2+, which form 1:2(ligand:cation) complexes with L3. Electrochemical recognition competition experiments suggest that L1 exhibits selective recognition for Mg2+ cation, while both L2 and L3 can recognize Cu2+ cation in the presence of large of other transition or post-transition metal cations.Optically active chiral ferrocenylimines 4 were prepared from L-Valinol with formylfeerocene and acetylferrocene, respectively, in the presence of p-TsOH in anhydrous benzene at room temperature. The reaction of compounds 4 with LiaPdCLt in the presence of sodium acetate produced cyclopalladated complexes 5, which were treated with PPha to give monomeric cyclopalladated compounds 6. All of the compounds were characterized by elemental analysis, IR and 1H NMR spectra.