Synthesis Of MCM-41-supported Palladium And Ruthenium Complexes And Studied Their Catalytic Properties In C-P?C-Se And Semihydrogenation Of Internal Alkynes

In this dissertation, we investigated applications of functionalized MCM-41-immobilized ruthenium and palladium complexes in the C-Se, C-P bond formation reactions and the semihydrogenation of internal alkynes. The whole work consists of three parts:1. MCM-41-immobilized bidentate nitrogen ruthenium(III) complex(MCM-41-2NRu Cl3) was prepared by the reaction of bidentate nitrogen-functionalized MCM-41(MCM-41-2N) with Ru Cl3 in acetone and characterized by XRD and EDS. We studied the catalytic properties of the MCM-41-2N-Ru Cl3 in the reaction of diaryl diselenides with alkyl halides in the presence of zinc dust. The results showed that reactions of diaryl diselenides with various alkyl halides proceeded smoothly in the presence of MCM-41-2N-Ru Cl3 and zinc dust, giving a variety of unsymmetrical diorganyl selenides in good to excellent yields. This novel supported ruthenium catalyst can be easily recovered by simple filtration and reused several times without signification loss of activity.2. MCM-41-immobilized bidentate nitrogen palladium(II) complex [MCM-41-2NPd(OAc)2] was prepared by the reaction of MCM-41-2N with Pd(OAc)2 in acetone. We investigated its catalytic properties in transfer semihydrogenation of internal alkynes. The results indicated that, in the presence of MCM-41-2N-Pd(OAc)2 and KOH, a variety of internal alkynes underwent the transfer semihydrogenation in DMF effectively, affording the corresponding(Z)-alkenes with high stereoselectivity in good to excellent yields. This heterogeneous palladium catalyst can be easily recovered and recycled for many times without significant loss of activity.3. The three-component condensation reaction of 3-aminopropyltriethoxysilane with diphenylphosphine and paraformaldehyde afforded triethoxysilyl-functionalized bidentate phosphine ligand, which was reacted with MCM-41 in toluene to afford a diphosphino-functionalized MCM-41(MCM-41-2P). The MCM-41-immobilized bidentate phosphine palladium(0) complex [MCM-41-2P-Pd(0)] was prepared by the reaction of MCM-41-2P with Pd(OAc)2 and then the reduction with hydrazine hydrate. We investigated its catalytic properties in the C–P coupling reaction of diphenylphosphine with aryl iodides. The results showed that this heterogeneous palladium catalyst exhibited high catalytic activity and could be reused for many times without significant loss of activity, which providing a convenient and practical route to the synthesis of a variety of functionalized triphenylphosphines.