Engineering Corrole and Porphyrin-Based Multivariate Metal–Organic Frameworks for Si–H Bond Insertion

As a contracted porphyrin analogue, corrole shows a more acidic and trinegative/triprotic nature compared with porphyrin in the field of coordination chemistry. However, the direct introduction of corrole into a metal–organic framework is quite difficult due to its lower C2V symmetry. Herein, we report the one-pot synthesis of a series of corrole and porphyrin-based multivariate porphyrinic metal–organic frameworks M1(TCPC)@M2-PCN-222 (M1 = CuIII, MnIII, FeIVCl; TCPC = 5,10,15-tris(4-carboxyphenyl) corrole; M2 = CoII, CuII, NiII, FeIIICl) and applied them to the insertion of a Si–H bond with α-diazoacetates. The resultant FeCl(TCPC)@Ni-PCN-222 displayed the highest efficiency with a turnover number of 796 based on the amount of Fe, which could be reused at least 5 times without a negligible loss of activity. Mechanistic studies disclosed that the reactivity of FeCl(TCPC)@Ni-PCN-222 came from the synergistic effect between FeCl(TCPC) and Ni-PCN-222, in which FeCl(TCPC) acted as the active site in the formation of metal-carbene, whereas Ni-PCN-222 helped condense the silane molecules for boosting the insertion of the Si–H bond.