Engineering\nCorrole and Porphyrin-Based Multivariate\nMetal–Organic Frameworks for Si–H Bond Insertion

As a contracted porphyrin analogue,\ncorrole shows a more\nacidic\nand trinegative/triprotic nature compared with porphyrin in the field\nof coordination chemistry. However, the direct introduction of corrole\ninto a metal–organic framework is quite difficult due to its\nlower <i>C</i><sub><i>2V</i></sub> symmetry. Herein,\nwe report the one-pot synthesis of a series of corrole and porphyrin-based\nmultivariate porphyrinic metal–organic frameworks M<sub>1</sub>(TCPC)@M<sub>2</sub>-PCN-222 (M<sub>1</sub> = Cu<sup>III</sup>, Mn<sup>III</sup>, Fe<sup>IV</sup>Cl; TCPC = 5,10,15-tris(4-carboxyphenyl)\ncorrole; M<sub>2</sub> = Co<sup>II</sup>, Cu<sup>II</sup>, Ni<sup>II</sup>, Fe<sup>III</sup>Cl) and applied them to the insertion of\na Si–H bond with α-diazoacetates. The resultant FeCl(TCPC)@Ni-PCN-222\ndisplayed the highest efficiency with a turnover number of 796 based\non the amount of Fe, which could be reused at least 5 times without\na negligible loss of activity. Mechanistic studies disclosed that\nthe reactivity of FeCl(TCPC)@Ni-PCN-222 came from the synergistic\neffect between FeCl(TCPC) and Ni-PCN-222, in which FeCl(TCPC) acted\nas the active site in the formation of metal-carbene, whereas Ni-PCN-222\nhelped condense the silane molecules for boosting the insertion of\nthe Si–H bond.