Synthesis,characterization Of Novel Triangular [Au₃]⁺ And Application In Hydroamination

Gold-containing organometallic complexes exhibit many excellent properties,mainly including wide applications in various homogeneous and heterogeneous catalysis,photoelectric materials,biopharmaceuticals and so on.Recently,the unique structures and aromaticity of the triangular all-metal complexes[Au₃]⁺and their wide application potentials in the field of catalysis have aroused wide research interest.This thesis mainly includes the following three research contents:1.The?₃-oxygen complex[?₃-O(PPh₃Au)₃]⁺BF₄^-was efficiently synthesized using chloro(triphenylphosphine)gold(PPh₃AuCl)monomer,and further reduced by carbon monoxide to prepare and separate the first PPh₃-stablized all-metal triangular complex[(PPh₃Au)₃]⁺BF₄^-,which has been fully characterized by Nuclear Magnetic Resonance(NMR),High Resolution Mass Spectrometry(HRMS),Infrared Spectroscopy(FT-IR)and Ultraviolet-Visible Absorption Spectroscopy(UV-Vis.)and Single-crystal X-ray diffraction etc.,and fully proved the composition and structure of this new triangular gold-containing complex.X-ray crystal structures showed that the[(PPh₃Au)₃]⁺BF₄^-complex was combined in the form of a dimer,and the six gold atoms form a bitetrahedral geometry with edge-sharing.2.The photochemical and electrochemical properties of the complexes[?₃-O(PPh₃Au)₃]⁺BF₄^-and[(PPh₃Au)₃]⁺BF₄^-were further studied.By testing the effects of temperature and solvent on the photochemical properties of the complexes,we found that the solid complexes[?₃-O(PPh₃Au)₃]⁺BF₄^-and[(PPh₃Au)₃]⁺BF₄^-both exhibited high sensitivity to temperatures.In solution,the complex[?₃-O(PPh₃Au)₃]⁺BF₄^-formed intermolecular hydrogen bonds with alcohol solvents,and the luminescence intensity was significantly enhanced;while the complex[(PPh₃Au)₃]⁺BF₄^-exhibited the strongest emission in comparative lower polar solvent dichloromethane.The results of cyclic voltammetry showed that both complexes exhibited a single oxidation process.3.These triangular all-metal complexes[?₃-O(PPh₃Au)₃]⁺BF₄^-and[(PPh₃Au)₃]⁺BF₄^-were applied to the hydroamination of terminal alkynes for the first time and exhibited highly reactivity,efficiency and regioselectivity.By optimizing the catalytic reaction conditions(catalyst type,catalyst amount,reaction substrate equivalent ratios,reaction temperature,reaction time,reaction gas atmosphere,etc.),the conversion of[Au₃]⁺catalyzed hydroamination reaction between phenylacetylene and aniline was reached quantitative(>99%).Furthermore,the reaction substrates were widely expanded,and the influence of electronic effects and steric hindrance on the reactivity and regioselectivity were investigated,and prepared various imine compounds,which was of great significance for the synthesis of a large number of natural anticancer drugs containing imine fragments.The mechanism of this triangle trigold complex catalyzed hydroamination of terminal alkynes was further explored.