Correction for 'Pseudo electron-deficient organometallics: limited reactivity towards electron-donating ligands' by Anaïs Pitto-Barry et al., Dalton Trans., 2017, 46, 15676-15683.
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http://dx.doi.org/10.1039/c9dt90235j | DOI Listing |
Angew Chem Int Ed Engl
December 2024
Saarland University, Coordination Chemistry, Campus C 4.1, 66123, Saarbrücken, GERMANY.
We report hitherto elusive side-on η2-bonded palladium(0) carbonyl (anthraquinone, benzaldehyde) and arene (benzene, hexa-fluorobenzene) palladium(0) complexes and present the catalytic hydrodefluorination of hexafluorobenzene by cyclohexene. The comparison with respective cyclohexene, pyridine and tetrahydrofuran complexes reveals that the experimental ligand binding strengths follow the order THF < C6H6 < C6F6 < cyclohexene < pyridine < benzaldehyde < anthraquinone. To understand this surprising order, the complexes' electronic structures were elucidated by nuclear magnetic resonance (NMR), single crystal X-Ray diffraction (sc-XRD), ultraviolet/visible (UV/Vis) electronic absorption, infrared (IR) vibrational, Pd L3-edge X-ray absorption (XAS), and X-ray photoelectron (XP) spectroscopic techniques, complemented by Density Functional Theory (DFT) calculations including energy decomposition (EDA-NOCV) and effective oxidation state (EOS) analyses.
View Article and Find Full Text PDFOrganometallics
October 2024
Department of Chemistry and Biochemistry, University of North Carolina at Greensboro, Greensboro, North Carolina 27402, United States.
The generation and functionalization of carbon- or nitrogen-centered radicals are of great interest for their potential synthetic utility. Here, we report the anaerobic electrocatalytic oxidation of two primary benzylic amines, benzylamine and 2-picolylamine, in the presence of a catalytic quantity of an electron deficient ferrocene derivative as a single-electron redox mediator. The use of the appropriate redox mediator prevented fouling of the electrode surface and significantly decreased the potential at which the catalytic oxidation reaction occurred.
View Article and Find Full Text PDFACS Macro Lett
November 2024
Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095, United States.
Org Biomol Chem
September 2024
School of Chemical Sciences, Indian Association for the Cultivation of Science, 2A & 2B Raja S.C. Mullick Road, Kolkata 700032, India.
C2-selectivity of unsubstituted indole over facile C3-substitution is attempted by utilizing the π-cavity of a nano-vessel made up of a palladium complex of an amino-ether heteroditopic macrocycle. Functional group tolerance (cyano, nitro, halo, ester, .), a broad substrate scope and outstanding selectivities with excellent yields (80-93%) of the desired products have been achieved in 12 h by maintaining all sustainable conditions like aqueous medium, recyclable catalyst, one-pot reaction, no external additives, mild temperature, .
View Article and Find Full Text PDFOrganometallics
June 2024
Department of Chemistry, Michigan State University, 578 South Shaw Lane, East Lansing, Michigan 48824, United States.
Ir-catalyzed C-H borylations of fluorinated and cyanated arenes with high -to-F/CN are described. Use of a dipyridyl hydrazone framework as the ancillary ligand and pinacolborane (HBpin) as the functionalizing reagent generates catalysts that are significantly more active selective than 4,4'-di--butyl-2,2'-bipyridine (dtbpy) for both electron-deficient and electron-rich substrates. Investigation of the ligand framework resulted in the observation of formal -borylation of the hydrazone by HBpin, as evidenced by NMR spectroscopy and X-ray crystallography.
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