Organometallic Ni(III) intermediates have been proposed in several Nickel-catalyzed cross-coupling reactions, yet no isolated bis(hydrocarbyl)Ni(III) complexes have been reported to date. Herein we report the synthesis and detailed characterization of stable organometallic Ni(III) complexes that contain two trifluoromethyl ligands and are supported by tetradentate N-donor ligands (R)N4 (R = Me or tBu). Interestingly, the corresponding Ni(II) precursors undergo facile oxidation, including aerobic oxidation, to generate uncommonly stable organometallic Ni(III) complexes that exhibit limited reactivity.
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http://dx.doi.org/10.1039/c4cc09594d | DOI Listing |
J Am Chem Soc
June 2024
Department of Chemistry and Biochemistry, University of California Los Angeles, Los Angeles, California 90095, United States.
Within the context of Ni photoredox catalysis, halogen atom photoelimination from Ni has emerged as a fruitful strategy for enabling hydrogen atom transfer (HAT)-mediated C(sp)-H functionalization. Despite the numerous synthetic transformations invoking this paradigm, a unified mechanistic hypothesis that is consistent with experimental findings on the catalytic systems and accounts for halogen radical formation and facile C(sp)-C(sp) bond formation remains elusive. We employ kinetic analysis, organometallic synthesis, and computational investigations to decipher the mechanism of a prototypical Ni-catalyzed photochemical C(sp)-H arylation reaction.
View Article and Find Full Text PDFOrganometallics
March 2024
Department of Chemistry, Lehigh University, 6 E Packer Ave., Bethlehem, Pennsylvania 18015, United States.
The interaction of tetramethylammonium acetate with [(MeCN)Ni(CF)], [(MeCN)Ni(CF)], and [NMe][(MeCN)Ni(CF)] was explored by F NMR spectroscopy. We show that depending on the nature of the nickel complex, one or two acetate ligands can add to the metal center and replace the nickel-bound MeCN ligands, depending on the acetate concentration. The number of acetates that could bind to nickel, and whether the resulting complex exists as a monomer or dimer, was determined to be dependent on the nature of the fluoroalkyl ligand.
View Article and Find Full Text PDFAcc Chem Res
November 2023
Department of Applied Chemistry, Faculty of Engineering, and Research Center for Environmental Preservation, Osaka University, 565-0871 Osaka Japan.
ConspectusThe development of functionalization reactions involving the activation of C-H bonds has evolved extensively due to the atom and step economy associated with such reactions. Among these reactions, chelation assistance has been shown to provide a powerful solution to the serious issues of reactivity and regioselectivity faced in the activation of C-H bonds. The vast majority of C-H functionalization reactions reported thus far has involved the use of precious metals.
View Article and Find Full Text PDFNat Commun
February 2023
Department of Chemistry, University of Illinois at Urbana-Champaign, 600 S. Mathews Avenue, Urbana, IL, 61801, USA.
Significant progress has been made in the bioinorganic modeling of the paramagnetic states believed to be involved in the hydrogen redox chemistry catalyzed by [NiFe] hydrogenase. However, the characterization and isolation of intermediates involved in mononuclear Ni electrocatalysts which are reported to operate through a Ni cycle have largely remained elusive. Herein, we report a Ni complex (NCHS2)Ni(OTf)2, where NCHS2 is 3,7-dithia-1(2,6)-pyridina-5(1,3)-benzenacyclooctaphane, that is an efficient electrocatalyst for the hydrogen evolution reaction (HER) with turnover frequencies of ~3,000 s and a overpotential of 670 mV in the presence of trifluoroacetic acid.
View Article and Find Full Text PDFJ Am Chem Soc
March 2022
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
The oxidative addition of aryl halides to bipyridine- or phenanthroline-ligated nickel(I) is a commonly proposed step in nickel catalysis. However, there is a scarcity of complexes of this type that both are well-defined and undergo oxidative addition with aryl halides, hampering organometallic studies of this process. We report the synthesis of a well-defined Ni(I) complex, [(bpy)NiCl] ().
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