Study On Synthesis And Reaction Of Mono And Hetero Nucleus Titanocene Complexes In Mild Condition

Titanocene derivatives have received considerable attention due to their potential as highly active and selective polymerization catalyst precursors, hydrogenation and isomerization, antitumour and antioxidative action. A series aromatic acid titanocene and hetero nucleus titanocene derivatives which contains mercury have been prepared and characterized. The main contents of this dissertation are as follows:1. Based on the concept of enhancing the ability of forming complex of ligand, a new approach for synthesizing titanocene derivatives catalyzed by supramolecular is presented herein. The feasibility of this approach was demonstrated using the reaction of forming titanocene derivatives in two phase (H₂O/CHCl₃) system catalyzed by water soluble β-cyclodextrin polymer. Based on the electronic absorption spectra and fluorescence spectra, it was found that p-cyclodextrin polymer is present as a microreactor in the reaction system, it selects ligand firstly in the aqueous phase to form a supramolecular complex, making ligand more active and reacts interfacially with titanocene dichloride in the organic phase more easily to form titanocene complex. Then, the next ligand substitutes for the titanocene complex and enter the microreactor, thus making the reaction to continue. At the same time, it was found that water soluble P-cyclodextrin polymer can enhance the stability of the species of titanocene ("Cp2Ti") and form titanocene complexes at pH = 10.60.2. New approach for synthesizing titanocene derivatives catalyzed by alcohol is presented herein. Based on the electronic absorption spectra, the reaction mechanism of preparing substitute salicylato titanocene complexes catalyzed by alcohol was discussed in detail. Influences of alcohols and sodium hydroxide on the reaction were also studied respectively. The optimal conditions for preparing titanocene complexes using this method were confirmed. Four substitude salicylato titanocene complexes were prepared by using ethanol as catalyst. The complexes were characterized by elemental analysis, IR and ¹H NMR spectra.3. 5,5'-dithiodisalicylic acid and 5-mercaptosalicylic acid were prepared by using salicylic acid as raw materials. 5-mercaptosalicylic acid reacts with mercury chloride to form [(2-OH-C₆H₃COOH-5-)S]₂Hg(II) and (2-OH-C₆H₃COOH-5-)SHg(H)Cl. A hetero...