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

Abstract

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 C 2V symmetry. Herein, we report the one-pot synthesis of a series of corrole and porphyrinbased multivariate porphyrinic metal−organic frameworks M 1 (TCPC)@ M 2 -PCN-222 (M 1 = Cu III , Mn III , Fe IV Cl; TCPC = 5,10,15-tris(4carboxyphenyl) corrole; M 2 = Co II , Cu II , Ni II , Fe III Cl) 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.