Synthesis And Application Of Porous Organic Polymer-bound N-heterocyclic Carbine Metal Complexes And Chrial Monodentate Phosphorus Ligand Metal Complexes

N-heterocyclic carbene ligand metal complexes and chiral monodentate phosphorus ligand metal complexes play an important role in organometallic chemistry.The emerging porous organic polymers(POPs)have showed great stability in heterogeneous catalysis.The aim of this paper is to realize the recycling of aforementioned two kinds of catalysts.We modified these two types of precious ligands with specific functional groups and then integrated them into the backbones of POPs.By using this method,we could take advantages of POPs to the greatest extent meanwhile the catalysts could recycled for up to five runs without significant loss in catalytic performance.The specific work is as follows:1)Three different kinds of N-heterocyclic carbene ligand metal(copper,silver,gold)complexes 6 were synthesized with the allyl functionalized imidazolium salt 5 and corresponding metal active species.These alkenyl functionalized N-heterocyclic carbene metal complexes 6 undergo radical polymerization with divinylbenzene(DVB)to constitute the catalyst---POP supported N-heterocyclic carbene metal complexes POP-NHC-M(Cu/Ag/Au)---by solvothermal synthesis.For each kind of the above catalysts,we adjusted the mass ratio between N-heterocyclic carbene complexes and DVB to prepare four different samples.The metal content in each catalyst was measured by ICP.The results tested by N2 isothermal desorption,SEM and TEM showed that the target catalyst is a kind of amorphous porous material with large surface area and pore volume.Additionally,the excellent thermostability of the catalysts was characterized by thermogravimetric analysis method.The three kinds of target catalysts showed good catalytic performance in the corresponding template reaction and could be recovered and reused for at least 5 times while maintaining their high catalytic activity.2)The chiral monodentate phosphine ligand 7 was at the outset modified with a styryl,and then copolymerized with DVB to form POP-bound chiral monodentate phosphine ligand(POP-CMP).The results tested by N2 isothermal desorption,SEM and TEM indicated that the POP-CMP is a type of amorphous porous material with large surface area and pore volume.However it is found that the target catalyst is deactive in model reaction through the preliminary study.The POP-CMP was oxidized during the cross-linking polymerization by further investigating the deactivation reason of the catalyst by solid-state 31PNMR spectroscopy.