Precise immobilization of metal single atoms into a porphyrinic metal-organic framework for an efficient alkene hydrosilylation  

作　　者：Chun-Ying Chen Qi-Jie Mo Fu-Zhen Li Hai-Li Song Li Zhang 

机构地区：[1]MOE Laboratory of Bioinorganic and Synthetic Chemistry,Lehn Institute of Functional Materials,School of Chemistry,Sun Yat-Sen University,Guangzhou 510006,China

出　　处：《Nano Research》2024年第7期5914-5921,共8页纳米研究（英文版）

基　　金：the National Natural Science Foundation of China(Nos.22371306 and 21821003);Guangdong Basic and Applied Basic Research Foundation(No.2019B151502017).

摘　　要：Alkene hydrosilylation is one of the most concise and atom-economical methods to synthesize organosilicon molecules.Herein,we reported the precise immobilization of metal single atoms(M-SAs;M=Ru,Rh,Ir,Pd,Pt,and Au)into a porphyrinic metalorganic framework(MOF)of PCN-222(PCN=porous coordination network),and then applied the resultant MOF composites of M-SAs@PCN-222 to alkene hydrosilylation.Under solvent-free conditions,Pt-SAs@PCN-222 displayed an especially high catalytic efficiency with the turnover frequency up to 119 s−1 and the maximum turnover number of 906,250 at room temperature.Experimental and theoretical studies revealed that there existed strong interactions between Pt-SAs@PCN-222 and the substrates,which helped to condense the substrates in the cavities of the porous catalysts.Further density functional theory calculations and molecular dynamics simulations disclosed that PCN-222 could transfer electrons to Pt-SAs to enhance the silane oxidative addition and drive the reaction to proceed smoothly via Chalk–Harrod pathway.

关 键 词：alkene hydrosilylation single atom catalysts metal-organic frameworks precision chemistry synergistic catalysis 

分 类 号：O62[理学—有机化学]