Reconceptualizing the Ir^III Role in Metallaphotoredox Catalysis: From Strong Photooxidant to Potent Energy Donor Article Swipe

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Stephen DiLuzio , Lakshmy Kannadi Valloli , Max Kudisch , Daniel Chambers , Garry Rumbles , Obadiah G. Reid , Matthew J. Bird , Hannah J. Sayre ·

YOU? · · 2024 · Open Access · · DOI: https://doi.org/10.1021/acscatal.4c03350

Dual Ir^III/L_nNi^II metallaphotoredox catalyzed C(sp³)–C(sp²) cross-coupling reactions are widely assumed to proceed by photoinduced single electron transfer steps due to the highly oxidizing Ir^III* excited state (Ir^III = [Ir(dF(CF₃)ppy)₂(dtbbpy)]⁺[PF₆]^–; dF(CF₃)ppy = 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine; L_n = dtbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine). Using time-resolved absorption and emission spectroscopy, we reveal that energy transfer between Ir^III* and various LnNi^II precatalysts and intermediates with k_q ≥ 10⁸ M^–1 s^–1 also drives catalysis. Specifically, the excited states of L_nNi^II dihalide precatalysts/organometallic intermediates accessible by energy transfer appear to drive bond homolysis, halogen radical elimination, and reductive elimination reactions that facilitate formation of cross-coupled products. Energy transfer dynamics consequently circumvent the need for photoinduced electron transfer, thereby extending substrate scopes to coupling partners that cannot be oxidized by Ir^III*. Within a cross-electrophile coupling model reaction between 4-bromobenzotrifluoride and bromocyclohexane, energy transfer activates the L_nNi^II precatalyst at early reaction times before nucleophilic reductants are present. In the absence of Ir^III, direct excitation of L_nNi^II(Br)₂ also activates the precatalyst to form a L_nNi^II(Br)(Aryl) intermediate. To compare energy transfer and electron transfer kinetics, we determined rate constants for reductive quenching by Br^– (k_SET = 4.1 × 10⁸ M^–1 s^–1) and for the subsequent electron transfer from reduced Ir^III•– to L_nNi^II(Br)₂ (k_SET = 4.1 × 10⁷ M^–1 s^–1) using Stern-Volmer analysis and pulse radiolysis, respectively. Energy transfer rate constants are competitive with the electron transfer rate constants and energy transfer is a parallel pathway within metallaphotoredox catalysis. Exploiting the energy transfer mechanism, we demonstrate highly selective cross-electrophile coupling between 4-chlorobenzotrifluoride and bromocyclohexane to form exclusively cross-coupled product. Here, with alkyl-trifluoroborate nucleophiles that do not reductively quench IrIII* emission, transmetalation with L_nNi^II(Br/Cl)(Aryl) followed by energy transfer also drives excited state reductive elimination to form C(sp³)–C(sp²) cross-coupled product. Similarly, energy transfer rather than Ni^II oxidation drives C(sp²)–OR reductive elimination, despite the strongly oxidizing ability of Ir^III*. In total, these reactions demonstrate energy transfer processes from Ir^III* to L_nNi^II in metallaphotoredox catalysis that can unlock alternative reactive pathways.

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Chemistry

Photochemistry

Quenching (Fluorescence)

Concepts

Chemistry Photochemistry Electron transfer Reductive elimination Catalysis Quenching (fluorescence) Electrophile Reaction rate constant Nucleophile Kinetics Organic chemistry Fluorescence Quantum mechanics Physics

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Type: article
Language: en
Landing Page: https://doi.org/10.1021/acscatal.4c03350
OA Status: green
Cited By: 8
References: 65
Related Works: 10
OpenAlex ID: https://openalex.org/W4400741521

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DOI: https://doi.org/10.1021/acscatal.4c03350

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Title: Reconceptualizing the Ir^III Role in Metallaphotoredox Catalysis: From Strong Photooxidant to Potent Energy Donor

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Type: article

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Language: en

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Publication year: 2024

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Publication date: 2024-07-16

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Authors: Stephen DiLuzio, Lakshmy Kannadi Valloli, Max Kudisch, Daniel Chambers, Garry Rumbles, Obadiah G. Reid, Matthew J. Bird, Hannah J. Sayre

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Landing page: https://doi.org/10.1021/acscatal.4c03350

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OA URL: https://www.osti.gov/biblio/2426389

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Concepts: Chemistry, Photochemistry, Electron transfer, Reductive elimination, Catalysis, Quenching (fluorescence), Electrophile, Reaction rate constant, Nucleophile, Kinetics, Organic chemistry, Fluorescence, Quantum mechanics, Physics

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Cited by: 8

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Reconceptualizing the IrIII Role in Metallaphotoredox Catalysis: From Strong Photooxidant to Potent Energy Donor Article Swipe

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Reconceptualizing the Ir^III Role in Metallaphotoredox Catalysis: From Strong Photooxidant to Potent Energy Donor Article Swipe