The Synthesis Of Silica-supported Arsine Palladium Complexes And Their Applications In Organic Synthesis

This dissertation consists of two parts:Part one: A silica-supported monodentate arsine palladium(II) complex has been prepared from γ-chloropropyltriethoxysilane via immobilization on fumed silica, followed by reacting with potassium diphenylarsenide and palladium chloride. The polymeric arsine palladium(II) complex is an efficient catalyst for Heck carbonylation of aryl halides and can be reused without noticeable lose of catalytic activities. A silica-supported monodentate arsine palladium(0) complex has been prepared by the reduction of the silica-supported monodentate arsine palladium(II) complex with hydrazine hydrate. It was found that this polymeric arsine palladium(0) complex is a highly active and stereoselective catalyst for arylation of styrene or acrylic acid. Moreover, the polymeric arsine palladium(0) complex is an efficient catalyst for the carbonyl allylation of aldehydes and the coupling reaction of aryl halides with terminal alkynes or Grignard reagent. It can be reused without noticeable lose of catalytic activities.Part two: A silica-supported bidentate arsine palladium(II) complex was prepared from 4-oxa-6,7-dichloroheptyltriethoxysilane via immobilization on fumed silica, followed by reacting with potassium diphenylarsenide and palladium chloride. Its catalytic properties for Heck carbonylation of aryl halides were studied. A silica-supported bidentate arsine palladium(0) complex was prepared by the reduction of the silica-supported bidentate arsine palladium(II) complex with hydrazine hydrate and its catalytic properties for arylation of conjugated alkenes were investigated. It was found that they show high catalytic activities for above-mentioned reactions and can be reused with nearly no loss of catalytic activities.