Synthesis,Characterization And Transformation Of Copper-Based Metal Hydride Clusters

Metal nanoclusters protected by ligands have a clear atomic structure.Their structures and molecular formulas can be determined by X-ray single crystal diffraction,mass spectrometry and other characterization techniques,so they become an ideal model system for the study of coordination chemistry of metal nanoparticles.In recent decades,copper nanoclusters have attracted the attention of researchers.The research mainly focused on the development of synthesis methodology,structural characterization and performance of copper nanoclusters.Different from most gold and silver nanoclusters,copper has a strong binding ability with hydrogen anion.NaBH4 or silane used in the synthesis of copper nanoclusters can easily lead to the introduction of hydrogen anion.These hydrogen anions also often give copper nanoclusters some unique catalytic properties and chemical reaction activity.Therefore,this paper focuses on the synthesis,structural characterization(determination of the position of hydrogen containing anion)and conversion chemistry of copper containing metal hydride clusters protected by novel phosphine ligands.The main research contents are as follows:1.Synthesis,structural characterization and application of phosphine ligand protected copper-based metal hydride clusters:single phosphine ligand protected[Cu21 H19(PPh3)4(Dppy)6]2+nanoclusters(PPh3=triphenylphosphine,Dppy=diphenyl2-pyridylphosphine).The accurate molecular composition and structure(including the exact positions of 19 hydrogen anions)were determined by X-ray single crystal diffraction and ESI-MS.Furthermore,the electrochemical test showed that[Cu2iH19]2+nanocluster showed better sensing performance in H2O2 detection.2.Conversion chemistry of phosphine ligand protected copper-based metal hydride clusters:using[Cu21H19]2+ nanoclusters as precursors,it was found that negative hydrogen ions on[Cu21H19]2+ could react with phenylacetylene to produce Cu25(PA)17(Dppy)3 nanoclusters(PA=Phenylacetylene anion).During the conversion process,the phenylacetylene undergoes hydrogenation reaction to become benzene ethylene.The[Cu21H19]2+nanoclusters can also react with phenylacetylene and triphenylphosphine palladium chloride to form[Cu2Pd2(Dppy)4(PA)].[Cu2Pd2(Dppy)4(DPB)]eutectic nanoclusters(DPB=1,4diphenylbutylene).During the conversion process,phenylacetylene is coupled to 1,4diphenylbutylene.