A stable scandium-terminal imido complex is activated by borane to form an unsaturated terminal imido complex by removing the coordinated Lewis base, 4-(dimethylamino)pyridine, from the metal center. The ensuing terminal imido intermediate can exist as a THF adduct and/or undergo cycloaddition reaction with an internal alkyne, C-H activation of a terminal alkene, and dehydrofluorination of fluoro-substituted benzenes or alkanes at room temperature. DFT investigations further highlight the ease of C-H activation for terminal alkene and fluoroarene. They also shed light on the mechanistic aspects of these two reactions.
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http://dx.doi.org/10.1021/ja5061559 | DOI Listing |
Dalton Trans
December 2024
Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin, Germany.
We report the proton-coupled electron transfer (PCET) reactivity of an octahedral Ta(V) aniline complex supported by an acridane-derived redox active NNN pincer ligand. The reversible binding of aniline to a Ta(V) dichloride induces significant coordination-induced bond weakening (CIBW) of the aniline N-H bonds. This enables a rare two-fold hydrogen atom abstraction, resulting in a terminal imido complex and a two-electron oxidation of the NNN pincer ligand, all while maintaining the metal's oxidation state.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Group of Coordination Chemistry, Institut des Sciences et Ingénierie Chimiques, École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland.
Lanthanide redox reactivity remains limited to one-electron transfer reactions due to their inability to access a broad range of oxidation states. Here, we show that multielectron reductive chemistry is achieved for ytterbium by using the tripodal tris(siloxide)arene redox-active ligand, which can store two electrons in the arene anchor. Reduction of the Yb(III) complex of the tris(siloxide)arene tripodal ligand affords the Yb(II) analogue by metal-centered reduction.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China.
The multi-electron redox chemistry of uranium(II) compounds remains largely unexplored. Herein, we report a series of two-electron oxidative atom and group transfer reactions at a well-defined uranium(II) center. The reactions of uranium(II) complexes [M][(TPBN)U] (M=K(2,2,2-cryptand) and K(18-crown-6)(THF)) with pyridine-N-oxide or nitrosobenzene, elemental sulfur/selenium or triphenylphosphine sulfide/selenide, and ditellurium salt led to the isolation of uranium(IV) terminal oxo and chalcogenido complexes [M][(TPBN)UX] (X=O, S, Se, Te).
View Article and Find Full Text PDFChemistry
November 2024
Pacific Northwest National Laboratory, Richland, Washington, 99345, United States of America.
Int J Biol Macromol
December 2024
Structural Biology Laboratory, School of Life Sciences, Jawaharlal Nehru University, New Delhi 110067, India. Electronic address:
Helicobacter pylori deoxyuridine triphosphate nucleotidohydrolase (HpdUTPase) is a key enzyme in the synthesis of the thymidine nucleotide pathway. It catalyzes the hydrolysis of dUTP to dUMP and releases pyrophosphate. This enzyme has been shown to be essential in several pathogenic organisms.
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