ArticleJournal of the American Chemical Society2024
Ultrafast Photophysics of Ni(I)-Bipyridine Halide Complexes: Spanning the Marcus Normal and Inverted Regimes.
Article in Journal of the American Chemical Society, 2024. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 6 papers.
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Who cites it
6 citing papers in PubMed.
- Site-Selective Distal Arylation of Sugars Enabled by Cyclic Acetals.Journal of the American Chemical Society · 2026Article
- Multireference Modeling Reveals the Origins of L‑Edge X‑ray Absorption Features in Photoredox-Active Nickel Complexes.The journal of physical chemistry. C, Nanomaterials and interfaces · 2026Article
- Decoding the Nested, Multicycle Mechanism of Ni-Catalyzed Redox-Neutral Cross-Coupling through Temperature Scanning Reaction Calorimetry.Journal of the American Chemical Society · 2026Article
- Selective arylation of atypical C-F bonds in polyfluoroarenes with aryl chlorides.Nature chemistry · 2025Article
- Reactivity Studies of Bipyridine-Ligated Nickel(I) and Nickel(0) Complexes Inform the Mechanism in Modern Cross-Coupling Reactions.Journal of the American Chemical Society · 2025Article
- Multiconfigurational Electronic Structure of Nickel Cross-Coupling Catalysts Revealed by X-ray Absorption Spectroscopy.The journal of physical chemistry letters · 2025Article
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Authors and funding
3 authors.
Funding
Abstract
Owing to their light-harvesting properties, nickel-bipyridine (bpy) complexes have found wide use in metallaphotoredox cross-coupling reactions. Key to these transformations are Ni(I)-bpy halide intermediates that absorb a significant fraction of light at relevant cross-coupling reaction irradiation wavelengths. Herein, we report ultrafast transient absorption (TA) spectroscopy on a library of eight Ni(I)-bpy halide complexes, the first such characterization of any Ni(I) species. The TA data reveal the formation and decay of Ni(I)-to-bpy metal-to-ligand charge transfer (MLCT) excited states (10-30 ps) whose relaxation dynamics are well described by vibronic Marcus theory, spanning the normal and inverted regions as a result of simple changes to the bpy substituents. While these lifetimes are relatively long for MLCT excited states in first-row transition metal complexes, their duration precludes excited-state bimolecular reactivity in photoredox reactions. We also present a one-step method to generate an isolable, solid-state Ni(I)-bpy halide species, which decouples light-initiated reactivity from dark, thermal cycles in catalysis.
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Registered trials
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