One-pot synthesis of multivariate porphyrinic metal-organic frameworks with the insertion of metallobipyridine and the cooperative catalysis for carbonyl hydrosilylation

A series of multivariate porphyrinic metal-organic frameworks with the insertion of bipyridine were obtained via one-pot synthesis. The single Pt site was introduced into the bipyridine linker of BPy@Co-PCN-224 through post-synthetic metalation. The resultant Pt(BPy)Cl2@M-PCN-224, especially when M was Co(II), could efficiently promote carbonyl hydrosilylation with a turnover number up to 13,140 based on Pt and could be recycled and reused for at least 6 times without a noticeable decrease of activity. Mechanistic studies based on in situ UV–vis, FT-IR and 1H NMR spectra, and kinetic isotope effect (KIE) experiments disclosed that the catalytic reaction was accomplished by the cooperative catalysis of Pt(BPy)Cl2 and Co-PCN-224, in which Pt(BPy)Cl2 was the catalytically active center and meanwhile the Co-PCN-224 could condense and increase the concentrations of ketone molecules in its inner cavities through the interactions between Co-porphyrin and carbonyl group. The plausible reaction pathway was proposed based on density functional theory calculations.