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)int...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.展开更多
基金the National Natural Science Foundation of China(Nos.22371306 and 21821003)Guangdong Basic and Applied Basic Research Foundation(No.2019B151502017).
文摘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.
