Synthesis Of Mcm-41-supported Bidentate Nitrogen Palladium(Ⅱ) And Bidentate Phosphine Rhodirm(Ⅲ) Complixes And Their Applications In Organic Synthesis

This dissertation consists of two parts:Part one:Dinitrogen-functionalized MCM-41 anchored palladium(II) complexes (MCM-41-2N-PdCl2 and MCM-41-2N-Pd(OAc)2) were conveniently prepared from 3-(2-aminoethylamino)propyltrimethoxysilane via immobilization on MCM-41, followed by reacting with palladium chloride or palladium acetate. These palladium complexes were characterized by XRD, XPS and elemental analysis. It was found that MCM-41-2N-PdCl2 can efficiently catalyze the allylation of aldehydes and ketones with allylic chlorides and the carbonylative Suzuki coupling reaction. We have also founded that the MCM-41-2N-Pd(OAc)2 exihibits high activity in the Suzuki reaction of aryl halides with arylboronic acids, giving a variety of biaryls in good to high yields. The novel supported bidentate nitrogen palladium catalysts can be easily recovered by simple filtration and reused many times without loss of activity.Part two:Diphosphino-functionalized MCM-41 anchored rhodium(Ⅲ) complex (MCM-41-2P-Rh(Ⅲ)) was conveniently synthesized from commercially available and cheap y-aminopropyltriethoxysilane via immobilization on MCM-41, followed by reacting with diphenylphosphinomethanol and rhodium chloride. The novel supported rhodium complex was characterized by XRD, XPS and elemental analysis. It was found that this complex exihibits high selectivity in addition reaction of alkynes with Ph2P(O)H, yielding the corresponding Trans products in high yields. This rhodium(III) complex can be easily recovered by simple filtration and reused many times without loss of activity.