Photoelectrochemical Fe/Ni cocatalyzed C−C functionalization of alcohols

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: June 19, 2024

Abstract The simultaneous activation of reactants on the anode and cathode via paired electrocatalysis has not been extensively demonstrated. This report presents a oxidative reductive catalysis based earth-abundant iron/nickel cocatalyzed C–C functionalization ubiquitous alcohols. A variety alcohols (i.e., primary, secondary, tertiary, or unstrained cyclic alcohols) can be activated at very low oxidation potential (~0.30 V vs. Ag/AgCl) photoelectrocatalysis coupled with versatile electrophiles. reactivity yields wide range structurally diverse molecules broad functional group compatibility (more than 50 examples).

Language: Английский

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Ultrafast Photophysics of Ni(I)–Bipyridine Halide Complexes: Spanning the Marcus Normal and Inverted Regimes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(22), P. 15506 - 15514

Published: May 22, 2024

Owing to their light-harvesting properties, nickel–bipyridine (bpy) complexes have found wide use in metallaphotoredox cross-coupling reactions. Key these transformations are Ni(I)–bpy halide intermediates that absorb a significant fraction of light at relevant reaction irradiation wavelengths. Herein, we report ultrafast transient absorption (TA) spectroscopy on library eight complexes, the first such characterization any Ni(I) species. The TA data reveal formation and decay Ni(I)-to-bpy metal-to-ligand charge transfer (MLCT) excited states (10–30 ps) whose relaxation dynamics well described by vibronic Marcus theory, spanning normal inverted regions as result simple changes bpy substituents. While lifetimes relatively long for MLCT first-row transition metal duration precludes excited-state bimolecular reactivity photoredox We also present one-step method generate an isolable, solid-state species, which decouples light-initiated from dark, thermal cycles catalysis.

Language: Английский

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Kinetics and Mechanism of PPh₃/Ni-Catalyzed, Zn-Mediated, Aryl Chloride Homocoupling: Antagonistic Effects of ZnCl₂/Cl^–

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(43), P. 29913 - 29927

Published: Oct. 18, 2024

The Ni/PPh

Language: Английский

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Regiodivergent Radical-Relay Alkene Dicarbofunctionalization

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(42), P. 28624 - 28629

Published: Oct. 10, 2024

Herein, we report a regiodivergent 1,n-dicarbofunctionalization of unactivated olefins enabled by Ni-catalyzed radical relay that forges both C(

Language: Английский

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Pyridine vs. Thiazole in Cyclometalated N^C^N Ni(II) Complexes

Inorganics, Journal Year: 2025, Volume and Issue: 13(2), P. 41 - 41

Published: Feb. 1, 2025

Six N^C^N cyclometalated Ni(II) complexes [Ni(N^C^N)Cl] or [Ni(N^C^N’)Br] with symmetric non-symmetric N^C^N’ ligands in which the peripheral N-groups were varied pyridine (Py), 4-thiazole (4Tz), 2-thiazole (2Tz), and 2-benzothiazole (2Btz) complementing previously reported di(2-pyridyl)phenide [Ni(Py(Ph)Py)X] X = Cl Br. The synthesized from NiBr2 N^CH^N’ protoligands through base-assisted nickelation, while received N^C(Cl)^N [Ni(COD)2] (COD 1,5-cyclooctadiene). Introduction of 4Tz on both sides shifted electrochemical gap ΔEexp Eox–Ered long wavelength UV-vis absorption maxima to higher energies, 2Tz leads a shift lower energies. When introducing only one as groups, remaining PhPy moiety dominates electronic properties electrochemistry photophysics are very similar Py(Ph)Py derivatives. In contrast this, introduction 2Btz shifts values regardless two groups character frontier molecular orbitals complexes, DFT calculations show. Long-wavelength absorptions vary 416 443 nm, their energies correlate well first reduction potentials. Negishi-type C–C cross-coupling reactions gave total yields ranging 1 60% 44%. reactivities roughly Facilitated (E around –2 higher) goes generally along improved performance, making thiazole-containing interesting candidates for such catalysis.

Language: Английский

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Protecting Group-Free Photocatalyzed O-Arylation of Quinic Acid

Tetrahedron Green Chem, Journal Year: 2025, Volume and Issue: unknown, P. 100070 - 100070

Published: Feb. 1, 2025

Language: Английский

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Nickel catalyzed C-N coupling of haloarenes with B2N4 reagents

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: April 3, 2025

Language: Английский

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Enantio- and Regioselective Ni-Catalyzed Radical Relay 1,4-Arylalkylation of 1,3-Enynes to Access Chiral Tetrasubstituted Allenes

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(18), P. 13940 - 13946

Published: Sept. 5, 2024

Language: Английский

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Ni-Catalyzed Kumada–Corriu Cross-Coupling Reactions of Tertiary Grignard Reagents and Bromostyrenes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(28), P. 6047 - 6052

Published: July 9, 2024

The development of protocols for the construction congested quaternary centers is highly sought-after. Herein, we report a method cross-coupling C(sp

Language: Английский

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