Heating a toluene solution of Cp*(CO)(C5H5N)FeSiMe2NPh2 led to insertion of pyridine into the iron-silicon bond to form Cp*(CO)Fe[eta3(C,C,C)-C5H5NSiMe2NPh2].
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http://dx.doi.org/10.1039/b308885e | DOI Listing |
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.
View Article and Find Full Text PDFInorg Chem
January 2025
School of Chemistry, Sun Yat-Sen University, Guangzhou 510006, China.
Regioselective -alkylation of benzotriazole is highly important to prepare biological materials. Herein, a series of AB-typed porphyrin and metalloporphyrin compounds were prepared. Catalytic results disclosed that Ir(III) pentafluorophenyl-substituted porphyrin promoted selective -alkylation of benzotriazole, and meanwhile, Fe(III) pyridine-substituted porphyrin accelerated -alkylation of benzotriazole.
View Article and Find Full Text PDFACS Omega
December 2024
Natural Products and Medicinal Chemistry Division, CSIR-Indian Institute of Integrative Medicine, Jammu 180001, India.
Formaldehyde has been used as a solvent and a source of carbon to insert a methylene group for bridging two imidazo[1,5-]pyridine molecules without using any metal catalysis. This strategy has been extended on other alkyl-, aryl-, and heteroaryl aldehydes as well. This C(sp)-C(sp)-H-C(sp) bond forming reaction proceeds via C(sp)H functionalization of imidazo[1,5-]pyridine and was applied on a wide range of substrates offering moderate to good yields of methylene-bridged/inserted bis-imidazo[1,5-]pyridines.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
School of Materials Science and Engineering, Department of Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, P. R. China.
Sulfurized polyacrylonitrile (SPAN) has emerged as a highly promising cathode material for next-generation lithium-sulfur (Li-S) batteries primarily due to its non-polysulfide dissolution and excellent cycle stability. Nevertheless, the specific roles and impacts of the pyrolyzed polyacrylonitrile, which constitutes the polymer backbone of SPAN, remain inadequately understood. In this study, comprehensive investigations from multiple aspects, including electrochemistry, spectroscopy, electron microscopy, and theoretical calculations, were conducted on a series of SPAN materials with various sulfur contents.
View Article and Find Full Text PDFAcc Chem Res
January 2025
Department of Chemistry, Northeast Normal University, Changchun 130024, China.
ConspectusIn the past decade, single-atom skeletal editing, which involves the precise insertion, deletion, or exchange of single atoms in the core skeleton of a molecule, has emerged as a promising synthetic strategy for the rapid construction or diversification of complex molecules without laborious synthetic processes. Among them, carbene-initiated skeletal editing is particularly appealing due to the ready availability and diverse reactivities of carbene species. The initial endeavors to modify the core skeleton of heteroarenes through carbon-atom insertion could date back to 1881, when Ciamician and Denstedt described the conversion of pyrroles to pyridines by trapping haloform-derived free carbene.
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