Precise immobilization of metal single atoms into a porphyrinic metal-organic framework for an efficient alkene hydrosilylation
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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 metal-organic 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.
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Precise immobilization of metal single atoms into a porphyrinic metal-organic framework for an efficient alkene hydrosilylation
)
Abstract
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 metal-organic 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.
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Acknowledgements
The authors acknowledge the support from the National Natural Science Foundation of China (Nos. 22371306 and 21821003) and Guangdong Basic and Applied Basic Research Foundation (No. 2019B151502017). We appreciate the support of TH-2 of National supercomputer center in Guangzhou.
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