Cooperative Catalytic Alkyne Hydrosilylation by a Porphyrinic Metal-Organic Framework Composite

Vinylsilanes are valuable building blocks and important structural units in organic chemistry. Herein, catalytic alkyne hydrosilylation was reported to be promoted by a porphyrin metal-organic framework with the incorporation of Pd nanoparticles (Pd@Ir-PCN-222). Catalytic results showed that Pd@Ir-PCN-222 displayed high catalytic efficiency, giving rise to the E isomer vinylsilane with an excellent turnover frequency (TOF) of 2564 h(-1). The mechanism studies revealed that the enhancement of the catalytic activity originated from the cooperation between iridium porphyrin and the Pd nanoparticle in confined spaces. The iridium porphyrin was prone to absorb and condense the hydrosilane and alkyne in the inner cavities of Ir-PCN-222, not only accelerating the reaction but also promoting the Pd nanoparticle to activate the Si-H and C equivalent to C bonds of hydrosilane and alkyne, respectively.

Automated summary

Vinylsilanes are important structural units in organic chemistry. This study reports a catalytic alkyne hydrosilylation method using a porphyrin metal-organic framework with incorporated Pd nanoparticles. The catalytic results show that the catalyst has high efficiency and selective production of E isomer vinylsilane. Mechanistic studies reveal that the cooperation between iridium porphyrin and Pd nanoparticles is the key to the high catalytic activity.