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Two porphyrin-based polymeric frameworks, SnP-BTC and SnP-BTB, as visible light photocatalysts for wastewater remediation were prepared by the solvothermal reaction of -dihydroxo-[5,15,10,20-tetrakis(phenyl)porphyrinato]tin(IV) (SnP) with 1,3,5-benzenetricarboxylic acid (HBTC) and 1,3,5-tris(4-carboxyphenyl)benzene (HBTB), respectively. The strong bond between the carboxylic acid group of HBTC and HBTB with the axial hydroxyl moiety of SnP leads to the formation of highly stable polymeric architectures. Incorporating the carboxylic acid group onto the surface of SnP changes the conformational frameworks as well as produces rigid structural transformation that includes permanent porosity, good thermodynamic stability, interesting morphology, and excellent photocatalytic degradation activity against AM dye and TC antibiotic under visible light irradiation.

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Dynamic Kinetic Activation of Aziridines Enables Radical-Polar Crossover (4 + 3) Cycloaddition with 1,3-Dienes.

J Am Chem Soc

January 2025

State Key Laboratory of Applied Organic Chemistry & College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China.

The cycloaddition of aziridines with unsaturated compounds is a valuable method for synthesizing nitrogen heterocycles. However, this process is predominantly substrate-controlled, posing significant challenges in regulating the regioselectivity of the C-N bond cleavage. In this study, we report a nickel-catalyzed dynamic kinetic activation strategy that enables catalyst-controlled activation of aziridines.

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Synthesis and Reactivity of a Bipyridyl Tantalum Complex.

Inorg Chem

January 2025

Testing and Analysis Center, Hebei Normal University, Shijiazhuang 050024, China.

The bipyridyl tantalum complex (2,6-PrCHO)Ta(bipy) () is synthesized by the reaction of (2,6-PrCHO)TaCl () and 2,2'-bipyridine in the presence of excess potassium graphite (KC). Complex coordinates readily with pyridine and 4-(dimethylamino)pyridine (dmap) to form Lewis base adducts (2,6-PrCHO)Ta(bipy)(L) (L = py (), dmap ()), and it exhibits rich redox reactivity toward small molecules: (a) single electron transfer (SET) occurs upon exposure of to phenyl sulfide or selenide dimer, giving the open-shell, bipy-centered radical complexes (2,6-PrCHO)Ta(bipy)(PhE) (E = S (), Se ()). (b) Regioselective C-C σ-bond formation via radical coupling is observed in the SET reaction of and aldehydes, ketones, or imines to furnish insertion products -, namely, sterically more crowded benzophenone, acetophenone, 2,6-dichlorobenzaldehyde, and benzophenone imine couple with C6 or C6' of bipy in , respectively, whereas sterically less hindered benzaldehyde, cyclohexanone, and benzylideneaniline couple with C2 or C2' of bipy, respectively.

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The steric hindrance effect of Co porphyrins promoting two-electron oxygen reduction reaction selectivity.

Chem Commun (Camb)

January 2025

Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119, China.

A new Co 5,10,15,20-tetrakis(2',6'-dipivaloyloxyphenyl)porphyrin (1) with eight ester groups in all and ' positions of phenyl groups was designed, which displayed significantly improved 2e oxygen reduction reaction (ORR) selectivity compared with a 5,10,15,20-tetrakis(-dipivaloyloxyphenyl) porphyrin (2) without large steric groups. This work is significant to reveal the steric hindrance effect of metal porphyrins on electrocatalytic ORR selectivity.

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A remarkably simple and efficient double defluorinative [3 + 3] annulation approach involving -phenyl-α-fluoro-α-phenylsulfonylacetamide and 2-CF-alkenes to access -phenyl-3,6-difluoropyridone derivatives has been achieved. The key to the success of this single-step synthesis of difluoropyridones is the strategic utilization of 2-CF-alkenes for consecutive allylic and vinylic substitution reactions and a desulfonylation cascade. We could also show that these difluoropyridones serve as a versatile platform for C-6-selective defluorinative functionalizations.

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