Synthesis Of Zirconium Phosphonate-Supported Palladium Catalysts And Application In The Homogeneous Suzuki Reaction

Transitional inetals-catalyzed Suzuki-Miyaura cross-coupling reaction is one of the most important methods for the construction of C-C bond.In recent years,in order to complete and optimization the Suzuki-Miyaura reaction’s conditions,much organic researchers had been paid and the excellent results had been obtained.In this thesis,using phenylglycine and phenylalanine as standing materials,the organosoluble zirconium phosphonates had been synthesized by several synthetic steps,in which the organic moieties of amino alcohols were covalently linked to the backbone oF zirconium phosphonate.After the partial modification of hydroxyl group in the internal and external surface by CIPPh₂ and the immobolization of Na₂PdCl₄ particles onto the the pores oF the backbone of zirconium phosphonate,zirconium phosphonate-supported palladium catalysts which were soluble in THF had been obtained.This type oF zirconium phosphonate-supported palladium catalysts 7a,b were soluble in THF with the good solubility（0.29-0.32 g/mL）.While the second solvent such as petroleum ether, n-hexane,cyclohexane and other nonpolarity solvent was added,the supported palladium catalysts quan（?）atively precipitate out from the homogeneous phase.The structure,chemical formulae and morphology of the supports 6a,b and palladium catalysts 7a,b had been characterized by IR,³¹p NMR.elemental analysis,TG,XPRD,N₂,adsorption-desorption isothermal curve,XPS,SEM and TEM.From X-PRD,N₂ adsorption-desorption isotherm,SEM and TEM images shown that this type of palladium catalysts was a hybrid polymer material with the layered,mesoporous and filiform structure（pore volume:0.3858 and 0.7307cc/g respectively）.The filiform structure was mutually twining to form the net structure with lengths up to hundreds of micrometers.The high catalytic activities in homogeneous Suzuki-Miyaura coupling reaction catalyzed by the palladium catalysts 7a,b in THF for 5 h at room temperature was achieved,at room temperature were observed.After the reaction was completed,the palladium catalysts 7a,b were quantitatively recovered and reused without the loss of catalytic activities for three times.