Perchloric Acid Silver Exists Polyphenyl Cyclopentadienyl Carbon - Carbon Bond Breaking Reaction

The reaction of polyphenylcyclopentadiene carbon-carbon cleavage with oxygen insertion is a novel discovery in organo-metallic chemistry field .The finding is more significance both to the synthesis of pyrylium salts with important practical applications and to the fundamental and theoretical studies on diversifying complex-metal catalyzing and oxidation. Basing on the reactions that 1,2.3,4-tetraphenylcyclopentadiene and 1,2,3,4,5-pentaphenylcyclopentadiene reacting with silver perchlorate and preparing pyrylium salts, the dissertation mainly studied the mechanism and general principle of the polyphenylcyclopentadiene carbon-carbon cleavage with 1,2,4-triphenylcyclopentadiene prepared by ourselves. The chief investigation as following:1. The preparation and characterization of the triphenylpyrylium saltsThe triphenylpyrylium salts and the optimum conditions have been obtained under the condition that the 1,2,4-triphenylcyclopentadiene and silver perchlorate as reactant, with the method of solvent diffusing and a series of different solvent proportion experiments. The prepared crystal has been characterized with X-ray single crystal diffraction, UV-Vis spectrum(UV-Vis), infrared spectrum(IR), nuclear magnetic resonance(NMR), mass spectrum(MS) and high performance liquid chromatography (HPLC).Through comparing the characterized results to the corresponding datum of tetraphenylpyrylium salts and pentaphenylpyrylium salts ,it can be witnessed the presence of pyrylium and fully proved the general principle of the prepared reaction of polyphenylcypyrylium with the polyphenylcyclopentadiene.2. The mechanism investigation of the prepared reaction of polyphenylpyryliumTo reveal the reaction mechanism, the reactant and reactionary conditions have been studied and witnessed their influence on the reaction process. The compared experiments of silver perchlorate and sliver trifluoroacetate proved the effect of Ag+ and counter-ion. The results indicated that the crystal reacting with silver perchlorate has been emerged quickly butnot emerged with sliver trifluoroacetate. The analyzed results of HPLC showed that the pyrylium salt has been also presented. In order to obtain more resultant to be used to related analyze, the pyrylium powder has been prepared with the general organic synthesis method. The mixture powder was analyzed by mass spectrum, HPLC and X-ray powder diffraction and the result indicated that pyrylium salt and metal silver were two components of the powder. In addition to, the absorbed water of reactant, diffused oxygen of air, solvent, solution acidity and substituted group numbers of ligand have been studied and investigated all the aspects acting with reaction process. 3. The application of HPLC in the synthesis of pyryliumThe earlier period trends of reaction can supply the information on the thermodynamics and dynamics and forecast the probability of crystal emerging by contrasting to the referred reaction. Utilizing the functions of the qualitative judge and quantitative analysis, the HPLC can trace the reaction trends. Thus a novel operational method has been established. The characterized ligand and crystal with NMR, MS, IR, UV-Vis and X-ray single crystal diffraction can be analyzed using the method and achieved the standard sample chromatography. At the same time, the diagram of peak area corresponding to resultant concentration and the diagram of resultant concentration corresponding to time have been also established. Basing on the datum can trace reaction, optimize reactionary conditions and forecast the results of reaction.