Since the first reports some three decades ago, the chemistry of pincer metal complexes has seen a tremendous development with impact on materials chemistry, supramolecular chemistry, bioorganometallics, and, presumably most significantly, on (catalytic) bond making and breaking processes. The remarkable progress is due to a large extent to the well-defined nature and tunability of the pincer ligand which allows the reactivity of the metal center to be modified and eventually tailored to specific needs. This Perspective summarizes the achievements in employing pincer complexes for mediating and catalyzing the cleavage of typically unreactive bonds such as C-H, C-C, C-E, and E-H bonds, arguably one of the most spectacular applications of pincer chemistry.
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http://dx.doi.org/10.1039/c1dt10339c | DOI Listing |
J Am Chem Soc
January 2025
Department of Chemistry, University of Wisconsin─Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States.
Aryl triflates make up a class of aryl electrophiles that are available in a single step from the corresponding phenol. Despite the known reactivity of nickel complexes for aryl C-O bond activation of phenol derivatives, nickel-catalyzed cross-electrophile coupling using aryl triflates has proven challenging. Herein, we report a method to form C(sp)-C(sp) bonds by coupling aryl triflates with alkyl bromides and chlorides using phenanthroline (phen) or pyridine-2,6-bis(-cyanocarboxamidine) (PyBCam)-ligated nickel catalysts.
View Article and Find Full Text PDFInorg Chem
January 2025
Department of Chemistry, The Johns Hopkins University, 3400 North Charles Street, Baltimore, Maryland 21218, United States.
The nonheme iron(II) complexes containing a fluoride anion, Fe(BNPAO)(F) () and [Fe(BNPAOH)(F)(THF)](BF) (), were synthesized and structurally characterized. Addition of dioxygen to either or led to the formation of a fluoride-bridged, dinuclear iron(III) complex [Fe(BNPAO)(F)(μ-F)] (), which was characterized by single-crystal X-ray diffraction, H NMR, and elemental analysis. An iron(II)(iodide) complex, Fe(BNPAO)(I) (), was prepared and reacted with O to give the mononuclear complex -Fe(BNPAO)(OH)(I) ().
View Article and Find Full Text PDFMol Divers
October 2024
Faculty of Pharmacy, Universiti Teknologi MARA Cawangan Selangor Kampus Puncak Alam, 42300, Bandar Puncak Alam, Selangor, Malaysia.
Transition-metal-catalyzed reductive cross-coupling is highly efficient for forming C-C bonds. It earns its limelight from its application by coupling unreactive electrophilic substrates to synthesize a variety of carbon-carbon bonds with various hybridizations (sp, sp, and sp), late-stage functionalization, and bioactive molecules' synthesis. Reductive cross-coupling is challenging to bring selectivity but promising approach.
View Article and Find Full Text PDFLangmuir
November 2024
Department of Chemistry, University of Massachusetts Lowell, Lowell, Massachusetts 01854, United States.
The reaction of l-cysteine and cysteamine hydrochloride with zinc oxide nanoparticles (ZnO NPs), by stirring excess reactant with the NPs in ethanol, has been studied by thermal gravimetric analysis (TGA), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and Raman spectroscopy. l-Cysteine adsorption occurs via the thiol functional group, and there is no evidence for bonding via the carboxylic acid or amine functionalities. However, Raman spectroscopy and XPS reveal some protonated thiol, suggesting unbound l-cysteine is also present, as confirmed by XRD that shows the presence of l-cysteine crystallites.
View Article and Find Full Text PDFPolymers (Basel)
September 2024
Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3 Street, 00-664 Warsaw, Poland.
At present, there are too few organ and tissue donors. Due to the needs of the medical market, scientists are seeking new solutions. Those can be found in tissue engineering by synthesizing synthetic cell scaffolds.
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