Synthesis And Characterization Of Water-Soluble Cobalt Complex And Polyfluorinated Aromatic Dithiocarbamic Acid Esters

The thesis is focused on the synthesis and characterization of water-soluble, glucose-Functionalized cobaloxime complexe and 2,3,5,6-tetrafluorobenzonitrile-substituted dithiocarbamic acid ester compounds. The main content is divided into two sections:1. Cobalt oxime complexes and their derivatives, as a class of good photo/electro hydrogen evolution molecular catalysts, have been pay intesive attention due to their many advantages, such as low overpotential, high turnover numbers?TONs? and turnover frequencies?TOFs? and the earth-abundant character. Although great achievements about the synthesis and modification of the cobaloxime molecular catalysts based on [Co??dmgH?₂Cl₂] have been achieved, the hydrogen production of most cobaloxime catalysts must be carried out in the presence of organic solvents and organic acids because of their insolubilities in acquesou solution. This manipulation in organic solvents will not only cause environmental pollution and waste, but also restrict the application of the catalysts in electrochemical water-splitting. In this section, we mainly aim to solve the problem of the water-solubility of cobaloxime complexes. In this section, we have developed a robust, inexpensive, and efficient glucose functionalized method to synthesize a water-soluble cobaloxime complex. The catalyst are systematically chacterized by using various methods such as NMR, HRMS, UV/Vis and IR spectroscopy. It is found that the as-synthesized glucose functionalized cobalt complex is a highly active and stable HER electrocatalyst for electrocatalytic water splitting under neutral pH conditions.2. Polyfluorinated aromatic compounds have found wide applications in medicinal chemistry and material science. At present, developing simple and efficient methods to constructing the new polyfluoroarenes-containing compounds is still challenged. It is known that the secondary amines can easily react with carbon disulfide to form dithiocarbamic acid anions in situ in the presence of base, followed by the SNAr reaction with nucleophilic receptor. By using this protocol, we choose the highly active pentafluorobenzonitrile as the nucleophilic receptor, and realize the simple, economic, efficient and highly selectivitive construction of 2,3,5,6-tetrafluorobenzonitrile-substituted dithiocarbamic acid esters via a one-pot two-step method. In addition, the polyfluoroarenes-containing compounds by the method of metal-free SNAr reactions are synthesized. Thus, compared with the metal-participated reactions, this strategy owns some advantages including simplity, cheapness and low toxicity. With this method, numerous secondary amines substitutions and N-H-containing heterocyclic compounds can generate corresponding desirable products in moderate to good yields.