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

Abstract

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≡C bonds of hydrosilane and alkyne, respectively.