Synthesis Of Porous Phosphine Ligand Polymers And Cobalt-Catalyzed Alkyne Hydrosilylation Reaction

This article is divided into two parts:the first part is the synthesis of vinyl-functionalized phosphine ligands and the application of heterogeneous catalysis with them;the second part is Co-catalyzed regio-and stereoselective hydrosilylation of alkynes with phosphine ligand.Chapter 1:Homogeneous metal catalysts are widely dominating organic reactions represented by hydroformylation,however the difficulties of separation and reuse can hardly be ignored.Porous organic polymers(POPs),thanks to their superior thermal stability,high surface area and large pore volume,have potential applications in the heterogeneous catalysis of numerous reactions.Vinyl-functionalized phosphine ligand porous polymer is an Effective Way to Realize Heterogeneous Catalysis of HydroformylationWe have developed new routes about the synthesis of two vinyl-functionalized phosphine ligands(tris(4-vinylphenyl)phosphine(Vinyl-PPh3)and 4,5-bis(4-vinylphenyl)phenylphosphine-9,9-dimethyl-xanthene(Divinyl-Xantphos)),which are copolymerized into POPs and then loaded with noble metal Rh.This catalyst is applied to catalysis of hydroformylation reaction,exhibiting excellent catalytic activity,selectivity as well as recyclability.Synthesis of vinyl-functionalized phosphine ligands has been successfully achieved through the new routes,with advantages of easily accessible reagent,greatly simplified steps and high total yield.Chapter 2:Hydrosilylation reaction has superior value in the academia,and huge application demand in the industry at the same time.The research on hydrosilylation catalysts has gone through the evolution from precious metals to 3d transition metals.Among numbers of metal catalysts,Cobalt catalysts take roles in different hydrosilylation reactions of various silanes and unsaturated hydrocarbons,because of their high activity,magnificentregio-and stereoselectivity,and cheap cost.We use Co(acac)2 as a catalyst and PPh3 as a ligand to catalyze hydrosilylation reaction of alkyneswithPhSiH3,which can generate trans anti-Markovnikov addition products((E)-?-vinylslianes).With its simple steps,easily available raw materials,mild reaction conditions,a wide range of substrates,wide functional groups tolerance and high regio-and stereoselectivity,this reactionwill be a powerful complement to the existing hydrosilylation studies.Then we use polymer POL-Xantphos&PPh3 as catalyst carrier and ligand to achieve heterogeneous Co-catalyzed hydrosilylation.The catalyst can efficiently catalyze the hydrosilylation reaction of acetylenes with diphenylsilanes and produce trans anti-Markovnikov addition products((E)-?).The method is easy to operate,with a wide range of substrates,high selectivity,and excellent cycle stability.This work extends the application of porous organic polymers heterogeneous catalysis of reactions.