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

Le résumé fourni par la source

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 porphyrin-based 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(4-carboxyphenyl) 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.

Ce résumé expose les affirmations des auteurs. BNTIC ne l’interprète pas comme une validation indépendante des résultats.