Dinuclear Pd complexes have found widespread applications as diverse catalysts for a multitude of transformations. Initially their ability to function as pre-catalysts for low-coordinated Pd species was harnessed in cross-coupling. Such Pd dimers are inherently labile and relatively sensitive to oxygen. In recent years, more stable dinuclear Pd -Pd frameworks, which feature bench-stability and robustness towards nucleophiles as well as recoverability in reactions, were explored and shown to trigger privileged reactivities via dinuclear catalysis. This includes the predictable and substrate-independent, selective C-C and C-heteroatom bond formations of poly(pseudo)halogenated arenes as well as couplings of arenes with relatively weak nucleophiles, which would not engage in Pd /Pd catalysis. This Minireview highlights the use of dinuclear Pd complexes as both pre-catalysts for the formation of highly active Pd and Pd -H species as well as direct dinuclear catalysts. Focus is set on the mechanistic intricacies, the speciation and the impacts on reactivity.
Download full-text PDF |
Source |
---|---|
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7898807 | PMC |
http://dx.doi.org/10.1002/anie.202011825 | DOI Listing |
Dalton Trans
January 2025
Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, School of Chemistry and Materials Science Heilongjiang University, 74 Xuefu Road, Harbin 150080, China.
Herein, we report the influence of solvent on the self-assembly of a dinuclear helicate, (NMe)[Eu(LR)]. A multiple species mixture with the chemical composition of [Eu(LR)] present in CHCN can be transformed into a helicate upon increasing the content of CHCl, accompanied by a significant enhancement in circularly polarized luminescence activity.
View Article and Find Full Text PDFNucleic Acids Res
January 2025
School of Chemical Sciences, Dublin City University, Glasnevin, Dublin 9, Ireland.
Copper compounds with artificial metallo-nuclease (AMN) activity are mechanistically unique compared to established metallodrugs. Here, we describe the development of a new dinuclear copper AMN, Cu2-BPL-C6 (BPL-C6 = bis-1,10-phenanthroline-carbon-6), prepared using click chemistry that demonstrates site-specific DNA recognition with low micromolar cleavage activity. The BPL-C6 ligand was designed to force two redox-active copper centres-central for enhancing AMN activity-to bind DNA, via two phenanthroline ligands separated by an aliphatic linker.
View Article and Find Full Text PDFInorg Chem
January 2025
Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education; Yunnan Provincial Center for Research and Development of Natural Products; School of Pharmacy, Yunnan University, Kunming 650500, P. R. China.
A series of dinuclear Ir(III) complexes have been constructed for enhanced photodynamic and photothermal therapy (PDT and PTT) for cisplatin-resistant non-small-cell lung cancer. They enter cells via caveolar endocytosis, target mitochondria but not nuclear, generate both singlet oxygen and superoxide anion, and release heat when exposed to infrared (IR) irradiation, thus inducing reactive oxygen species (ROS)-associated cell disruption and thermal ablation. The IR-generated ROS can further activate caspases, triggering apoptosis.
View Article and Find Full Text PDFChemistry
January 2025
National Tsing Hua University, Department of Chemical Engineering, 101, Sec 2, Kuang-Fu Rd., 300, Hsinchu, TAIWAN.
This study focuses on enhancing the water oxidation reaction (WOR) efficacy of dinuclear cobalt complex catalysts from both kinetic (turnover frequency, TOF) and thermodynamic (overpotential, η) perspectives. For this purpose, we synthesized six dinuclear cobalt complexes 1-6 comprising non-innocent ligands with different electronically active substituents (-OMe (1), -Me (2), -H (3), -F (4), -Cl (5), and -CN (6)). The electronic effects on the electrochemical WOR under neutral, acidic, and alkaline conditions were investigated experimentally and computationally.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
University of Oxford, Chemistry, 12 Mansfield Road, OX1 3TA, Oxford, UNITED KINGDOM OF GREAT BRITAIN AND NORTHERN IRELAND.
In homogeneous catalysis, uncovering structure-activity relationships remains very rare but invaluable to understand and rationally improve performances. Here, generalizable structure-activity relationships apply to a series of heterodinuclear polymerization catalysts featuring Co(III) and s-block metals M(I/II) (M= Na(I), K(I), Ca(II), Sr(II), Ba(II)). These are shown to apply to polycarbonate production by the ring-opening copolymerizations (ROCOP) of cyclohexene oxide (CHO) and carbon dioxide (CO2), conducted at high (20 bar) and low (1 bar) CO2 pressures, and to polyester production by copolymerization of cyclohexene oxide and phthalic anhydride (PA).
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!