Construction And Catalysis Of Metal-organic Complexes Based On Triphenylphosphine

The metal-organic supramolecular assemblies usually has a closed structure,a limited adjustable window,and a clear internal and external environment.By encapsulating the guest molecule,the electron transfer rate is accelerated,the electron transfer path is controlled,and the charge separation efficiency is improved.Object properties have important applications in the fields of molecular recognition,selective catalysis,biomedicine,and photosensitive materials.On the other hand,triphenylphosphine has a strong binding ability with transition metals,and the phosphorus atom on triphenylphosphine can regulate the catalytic activity and selectivity of metal ions,thereby improving the reaction efficiency.Therefore,the complex of triphenylphosphine and metal is also widely used in the field of catalysis.The coordination of triphenylphosphine and transition metal can be used as a module for assembling supramolecules,and the directional design and assembly of the desired supramolecular ordered structure.?1?In the second chapter of the paper,by using 2-phenylphosphine benzaldehyde as the functional control unit,with transition metal Pd?II?ions as the metal center,and 1,3,5triaminotriphenylamine structure control unit,Design and synthesis of metal-organic octahedral Pd-TPA.The octahedral Pd-TPA is used in the hydrogenation reaction of alkyne.In the semi-hydrogenation reaction of diphenylacetylene,the conversion rate of cis stilbene can reach 95.4%,cis stilbene compared to trans stilbene The selectivity can reach 98.7%;in the hydrogenation reaction of phenylacetylene,the complex Pd-TPA can also play a very good hydrogenation effect.The reduction of carbon-carbon triple bond is a very important reaction in synthetic organic chemistry.Adding an equivalent amount of hydrogen molecules to the triple bond stereoselectively,the conversion of alkyne to olefin?ie,semi-hydrogenation?can be achieved,and?E?-or?Z?-olefin can be selectively prepared.It is of great practical significance to apply the metal-organic cage structure to the hydrogenation reaction of alkyne to realize the efficient and selective conversion of the reaction.?2?In the third chapter of the paper,isophthalic acid is used as the structural control unit,and the functional adjustment unit 2-phenylphosphine benzaldehyde is coordinately connected through the amide bond to obtain the two-arm tridentate ligand DTP,and Transition metal Co?II?ion coordination self-assembly to obtain metal-organic three-membered ring Co-DTP.The complex Co-DTP can achieve hydrogen production by photolysis,indicating that it can catalyze proton reduction.To further study the application of cobalt complexes in the photocatalytic reaction of C-S bond coupling dehydrogenation to benzothiazole,for most substrates,the catalytic process can be completed with a high conversion rate within 1h reaction time,and the reaction The process simultaneously realizes the processes of oxidative coupling and hydrogen reduction,fully embodying the concept of green chemistry.The traditional reaction to construct C-C and C-X bonds generally requires stoichiometric metal reagents and organic halides as raw materials,and is accompanied by stoichiometric salts as by-products.In the field of organic photosynthesis,light energy is used as the direct energy source,and the dual catalyst system constructed by the photocatalyst/catalyst catalyzes the dehydrogenation of the C-X bond to form H₂ as a by-product.This type of reaction requires no external oxidant or stoichiometric sacrificial agent.It can realize the formation or aromatization of C-C and C-X bonds,and has the advantages of high atomic economy,high efficiency and environmental friendliness.