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http://dx.doi.org/10.1002/anie.201205795 | DOI Listing |
Chemistry
January 2025
Jadavpur University, Chemistry, 188 Raja S. C. Mallick Road, 700032, Kolkata, INDIA.
Two π-radical complexes containing bisazo-aromatic-centered radical anion (1•-) were synthesized through in-situ electron transfer from metal-to-ligand using [IrI] and 2-(2-Pyridylazo)azobenzene (1) in inert hydrocarbon solvent. These are characterized as diradical [IrIII(1•-)2]+[2]+ and monoradical [IrIII(1•-)Cl2(PPh3)] 3. In contrast, a rare metal-mediated hydrolytic cleavage of the C(sp2)-N bond occurred in protic solvent resulting in quaternary radical complex [IrIII(1•-)(1')(PPh3)]+(4)+.
View Article and Find Full Text PDFTransition metal-mediated catalytic reduction, oxidation, and hydrofunctionalization reactions are important organic reactions and are considered highly atom-economical. Owing to their unique properties, selenium ligated several transition metals-based complexes have been reported for several catalytic applications. This review presents the synthesis of various selenium-supported transition metal complexes and their catalytic applications in reduction, oxidation, N-alkylation of amines, and hydrofunctionalization reactions.
View Article and Find Full Text PDFDalton Trans
January 2025
Department of Chemistry, University of Alberta, 11227 Saskatchewan Dr, Edmonton, Alberta, T6G 2G2, Canada.
This article provides an alternative pathway towards cyclosilapentenes (, SiH2-iPr and SpiroSi) involving the use of Rieke magnesium to activate the requisite dienes for synthesis. Subsequent metal-mediated dehydrocoupling of cyclosilapentene and mixtures with another cyclogermapentene gives oligomers with backbone Si-Si (number average molecular weight, = 1.0 kDa) and Si-Ge ( = 1.
View Article and Find Full Text PDFInorg Chem
January 2025
Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQSO-Centro de Investigación en Química Sostenible and Departamento de Química, Universidad de Huelva, 21007 Huelva, Spain.
Phosphinoazide complexes of the composition TpM-L (M = Cu, Ag, and L = 2-azido-1,3-bis(2,6-diisopropylphenyl)-2,3-dihydro-1-1,3,2-diazaphosphole) have been synthesized and structurally characterized. Their thermal decomposition led to cyclodiphosphazenes as a result of the metal-mediated coupling of two nitrene units in a process that takes place in both a stoichiometric and catalytic manner. Experimental data have allowed proposing a mechanistic pathway for this new transformation.
View Article and Find Full Text PDFJ Phys Chem B
January 2025
Department of Chemistry and Biochemistry, University of Lethbridge, 4401 University Drive West, Lethbridge, Alberta, Canada T1K 3M4.
Despite the remarkable resistance of the nucleic acid phosphodiester backbone to degradation affording genetic stability, the P-O bond must be broken during DNA repair and RNA metabolism, among many other critical cellular processes. Nucleases are powerful enzymes that can enhance the uncatalyzed rate of phosphodiester bond cleavage by up to ∼10-fold. Despite the most well accepted hydrolysis mechanism involving two metals (M to activate a water nucleophile and M to stabilize the leaving group), experimental evidence suggests that some nucleases can use a single metal to facilitate the chemical step, a controversial concept in the literature.
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