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

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 6, 2024

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

Language: Английский

Phenylphosphonic acid corroles: corroles that link, corroles that bind

Dalton Transactions, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 30, 2024

Thanks to the presence of a phosphonic acid group, A 2 B-corroles were covalently linked Zr clusters PCN-222 MOF. After insertion Co, cobalt corroles are able bind CO with high selectivity vs. , N and O .

Language: Английский