Reaction of [Ru(OAc)2(PPh3)2] with a P-functionalized imidazolium bromide easily affords a cationic abnormal carbene Ru system. Metalation with Ag2O yields a Ru-Ag complex containing an anionic dicarbene ligand, while subsequent transmetalation with Au(tht)Cl leads to the corresponding Ru-Au system. The bimetallic complexes were characterized by single crystal X-ray diffraction and are the first examples of complexes bearing anionic dicarbene ligands connecting two different d-block elements.
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http://dx.doi.org/10.1039/c5dt01914a | DOI Listing |
J Am Chem Soc
January 2025
Department of Chemistry, Queen's University, Chernoff Hall, Kingston, Ontario K7L 3N6, Canada.
The use of gold nanoclusters in biomedical applications has been steadily increasing in recent years. However, water solubility is a key factor for these applications, and water-soluble gold nanoclusters are often difficult to isolate and susceptible to exchange or oxidation in vivo. Herein, we report the isolation of N-heterocyclic carbene (NHC)-protected atomically precise gold nanoclusters functionalized with triethylene glycol monomethyl ether groups.
View Article and Find Full Text PDFChembiochem
December 2024
Department of Biological, Chemical, and Pharmaceutical Sciences, Technologies, Università di Palermo, Viale delle Scienze Edificio 17, 90128, Palermo, Italy.
The most recurrent familial cause of amyotrophic lateral sclerosis (ALS) and frontotemporal dementia (FTD) is the presence of an abnormal number of intronic GGGGCC (GC) repetitions in the C9orf72 gene, which has been proposed to drive ALS/FTD pathogenesis. Recently, it has been shown that such GC repetitions can fold into G-quadruplex (G4) secondary structures. These G4s have been selectively stabilized by small-molecule binders, furnishing proof-of-principle that targeting these non-canonical nucleic acid sequences represents a novel and effective therapeutic strategy to tackle neurodegenerative disorders.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur, 741246, India.
Mesoionic compounds, with positive and negative charges, are expected to have dual-site highest occupied molecular orbital (HOMO, donor) and lowest unoccupied molecular orbital (LUMO, acceptor) reactivity. Herein, we report a novel class of air-stable mesoionic N-heterocyclic thiones (mNHTs) synthesized from abnormal N-heterocyclic carbenes (aNHCs). DFT studies revealed a highly polarized exocyclic thione moiety and computed Fukui function analysis suggests the dual-site HOMO/LUMO reactivity of mNHTs predicting donor property at the negatively charged 'S' center while acceptor property at the cationic imidazole ring.
View Article and Find Full Text PDFInorg Chem
October 2024
Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur 741246, West Bengal, India.
Cu-catalyzed carbonyl hydrosilylation involves a ligated "[(L)CuH]" as the active catalyst, where the ligand L has a crucial role toward the stability, stereoselectivity, and enhancement of the hydridicity. Strongly σ-donating N-heterocyclic carbenes (NHCs), their ring-expanded form, and an abnormal NHC as ligands have yielded robust and efficient Cu catalysts. However, cyclic(alkyl)(amino)carbenes (CAACs), despite being stronger σ-donors than NHCs and already having a salient Cu chemistry, are yet to be reported as a similar ligand platform for this purpose.
View Article and Find Full Text PDFRSC Adv
June 2024
Computational and Theoretical Chemistry Unit, Department of Chemistry, Faculty of Science, University of Douala P.O. Box 24157 Douala Cameroon
Bis-N-heterocyclic carbene ligands (bis(NHC)) have introduced a new approach to designing homogeneous and heterogeneous catalysts, demonstrating the versatility of ligand concepts in catalysis. This study presents a computational analysis of palladium (+ii and +iv) complexes containing either a normally (bis(nNHC)) or an abnormally (bis(aNHC)) bound CH-bridged bis-N-heterocyclic carbene ligand; in addition, ancillary ligands are permuted from chlorides (X = Cl) to bromides (X = Br). Density functional theory at the B3PW91/6-31G(d)/Lanl2DZ level in the gas phase was used to investigate the electronic structure and bonding properties of bis(NHC)PdX and bis(NHC)PdX for bis(NHC) palladium(ii) dihalide and palladium(iv) tetrachloride complexes, respectively.
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