Mechanisms of Photoredox Catalysis Featuring Nickel–Bipyridine Complexes

ACS Catalysis, Год журнала: 2024, Номер 14(11), С. 9055 - 9076

Опубликована: Май 29, 2024

Metallaphotoredox catalysis can unlock useful pathways for transforming organic reactants into desirable products, largely due to the conversion of photon energy chemical potential drive redox and bond transformation processes. Despite importance these processes cross-coupling reactions other transformations, their mechanistic details are only superficially understood. In this review, we have provided a detailed summary various photoredox mechanisms that been proposed date Ni-bipyridine (bpy) complexes, focusing separately on photosensitized direct excitation reaction By highlighting multiple key findings, depict how mechanisms, which ultimately define substrate scope, themselves defined by ground- excited-state geometric electronic structures Ni-based intermediates. We further identify knowledge gaps motivate future studies development synergistic research approaches spanning physical, organic, inorganic chemistry communities.

Язык: Английский

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Challenges and Future Perspectives in Photocatalysis: Conclusions from an Interdisciplinary Workshop

JACS Au, Год журнала: 2024, Номер 4(8), С. 2746 - 2766

Опубликована: Авг. 8, 2024

Photocatalysis is a versatile and rapidly developing field with applications spanning artificial photosynthesis, photo-biocatalysis, photoredox catalysis in solution or supramolecular structures, utilization of abundant metals organocatalysts, sustainable synthesis, plastic degradation. In this Perspective, we summarize conclusions from an interdisciplinary workshop young principal investigators held at the Lorentz Center Leiden March 2023. We explore how diverse fields within photocatalysis can benefit one another. delve into intricate interplay between these subdisciplines, by highlighting unique challenges opportunities presented each multidisciplinary approach drive innovation lead to solutions for future. Advanced collaboration knowledge exchange across domains further enhance potential photocatalysis. Artificial photosynthesis has become promising technology solar fuel generation, instance, via water splitting CO

Язык: Английский

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Catalysis in the Excited State: Bringing Innate Transition Metal Photochemistry into Play

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4665 - 4680

Опубликована: Март 5, 2025

Transition metal catalysis is an indispensable tool for organic synthesis that has been harnessed, modulated, and perfected many decades by careful selection of centers ligands, giving rise to synthetic methods with unparalleled efficiency chemoselectivity. Recent developments have demonstrated how light irradiation can also be recruited as a powerful dramatically alter the outcome catalytic reactions, providing access innovative pathways remarkable potential. In this context, adoption photochemical conditions mainstream strategy drive reactions unveiled exciting opportunities exploit rich excited-state framework transition metals applications. This Perspective examines advances in application complexes standalone photocatalysts, exploiting innate reactivity their excited states beyond common use photoredox catalysts. An account relevant examples dissected provide discussion on electronic reorganization, orbitals involved, associated different types states. analysis aims practitioners fundamental principles guiding strategies understand, design, apply light-activation homogeneous synthesis.

Язык: Английский

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The Multiple Roles of Bipyridine-Nickel(II) Complex in Versatile Photoredox C(sp²)–C(sp³) Cross-Coupling

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 3328 - 3338

Опубликована: Фев. 9, 2025

Язык: Английский

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Sulfonyl hydrazides as a general redox-neutral platform for radical cross-coupling

Science, Год журнала: 2025, Номер unknown

Опубликована: Март 6, 2025

Язык: Английский

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Dual Nickel- and Photoredox-Catalyzed Asymmetric Reductive Cross-Couplings: Just a Change of the Reduction System?

Accounts of Chemical Research, Год журнала: 2024, Номер 57(14), С. 1997 - 2011

Опубликована: Июль 4, 2024

ConspectusIn recent years, nickel-catalyzed asymmetric coupling reactions have emerged as efficient methods for constructing chiral C(sp

Язык: Английский

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Photodriven Ammonia Synthesis from N₂ and H₂: Recycling of a Molecular Molybdenum Nitride

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 27, 2025

The synthesis of ammonia from its elements, N2 and H2, is the most atom-economical thermodynamically preferred route but presents a high kinetic barrier thus rare using molecular compounds. Irradiation molybdenum nitride prepared cleavage with visible light in presence an iridium photocatalyst 1–4 atm H2 produced yields along formation cationic, formally molybdenum(VI) pentahydride as major molybdenum-containing product. Continued irradiation hydride under atmosphere resulted regeneration that was recycled used for additional hydrogenation to generate more ammonia, demonstrating superstoichiometric batch only compounds ambient conditions.

Язык: Английский

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New reactivity of late 3d transition metal complexes in catalytic reactions of alkynes

Chemical Society Reviews, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This review summarizes seven types of new reactivities found in late 3d metal complexes and catalytic examples recent years.

Язык: Английский

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Trendbericht Photochemie 2025

Nachrichten aus der Chemie, Год журнала: 2025, Номер 73(4), С. 56 - 67

Опубликована: Март 31, 2025

Abstract Dieser Trendbericht erläutert Erkenntnisse der letzten beiden Jahre aus Sicht von Wissenschaftlerinnen und Wissenschaftlern des interdisziplinären, durch die DFG geförderten Konsortiums Transregio 325. Die Autorinnen Autoren forschen vor allem zu chemischer Photokatalyse beleuchten besonders Themen mit molekülchemischer Komponente.

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Unraveling a Complex Mechanistic Picture of Photochemical Nickel-Catalyzed THF Arylation through Product Enantioselectivity Analysis

Synlett, Год журнала: 2025, Номер unknown

Опубликована: Май 6, 2025

Abstract This study provides a comprehensive mechanistic understanding of asymmetric THF α-O-arylation via Ni photochemical catalysis, leveraging enantioinduction data to refine the reaction pathway. Originally reported in racemic fashion by Molander and Doyle, this transformation was re-examined using chiral bis(oxazoline) ligands, revealing distinct enantioselectivity trends depending on halogen present aryl halide pre-catalyst. Stoichiometric experiments demonstrated that Ni(II) oxidative addition complex is primarily responsible for trapping radical, while multivariate linear regression modeling confirmed remains coordinated during enantiodetermining step. Time-course uncovered an alternative initial pathway when Ni(0) used as pre-catalyst, which ultimately converged main EPR analysis further revealed rapid comproportionation between Ni(II), forming Ni(I) species engage radical at early stages, accounting observed reactivity differences. By integrating with experimental techniques such spectroscopy, establishes powerful tool investigations catalysis. The insights gained not only our transformation, but also provide framework probing similar Ni/Ir dual photocatalytic systems. 1 Introduction 2 Enantioselectivity Data Highlights Complex Mechanistic Scenario 3 Probing Predominant Pathway Experiments 4 MLR Modeling Understand Halogen Effect Enantioinduction 5 Proposed Prevalent Mechanism 6 Initiation Precatalyst 7 Conclusion

Язык: Английский

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