Bottom‐Up Construction of Ni(II)‐Incorporated Covalent Organic Framework for Metallaphotoredox Catalysis DOI Open Access

Hai‐Chao Hu,

Zhipeng Wang, Lin Liang

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(10)

Published: Dec. 9, 2023

The construction of an all-in-one catalyst, in which the photosensitizer and transition metal site are close to each other, is important for improving efficiency metallaphotoredox catalysis. However, development convenient synthetic strategies precise catalyst remains a challenging task due requirement installation catalytic sites. Herein, we have successfully established facile bottom-up strategy direct synthesis Ni(II)-incorporated covalent organic framework (COF), named LZU-713@Ni, as versatile catalyst. LZU-713@Ni showed excellent activity recyclability photoredox/nickel-catalyzed C-O, C-S, C-P cross-coupling reactions. Notably, this displayed better than its homogeneous analogues, physically mixed dual system, and, especially, LZU-713/Ni was prepared through post-synthetic modification. improved should be attributed implementation strategy, incorporated fixed, ordered, abundant sites into framework. This work sheds new light on exploration concise effective multifunctional COF-based photocatalysts.

Language: Английский

Light-driven C–O coupling of carboxylic acids and alkyl halides over a Ni single-atom catalyst DOI
Mark A. Bajada, Giovanni Di Liberto, Sergio Tosoni

et al.

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(11), P. 1092 - 1103

Published: June 15, 2023

Language: Английский

Citations

46
Mechanisms of Photoredox Catalysis Featuring Nickel–Bipyridine Complexes DOI Creative Commons
David A. Cagan, Daniel Bím, Nathanael P. Kazmierczak

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 9055 - 9076

Published: May 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.

Language: Английский

Citations

24
Mechanism of Ni-Catalyzed Photochemical Halogen Atom-Mediated C(sp3)–H Arylation DOI
Alexander Q. Cusumano, Braden C. Chaffin, Abigail G. Doyle

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(22), P. 15331 - 15344

Published: May 23, 2024

Within the context of Ni photoredox catalysis, halogen atom photoelimination from has emerged as a fruitful strategy for enabling hydrogen transfer (HAT)-mediated C(sp3)–H functionalization. Despite numerous synthetic transformations invoking this paradigm, unified mechanistic hypothesis that is consistent with experimental findings on catalytic systems and accounts radical formation facile C(sp2)–C(sp3) bond remains elusive. We employ kinetic analysis, organometallic synthesis, computational investigations to decipher mechanism prototypical Ni-catalyzed photochemical arylation reaction. Our revise previous proposals, first by examining relevance SET EnT processes intermediates relevant HAT-based investigation highlights ability blue light promote efficient Ni–C(sp2) homolysis cationic NiIII reductive elimination bipyridine NiII complexes. However interesting, rates selectivities these do not account productive pathway. Instead, our studies support involves evolution in situ generated dihalide intermediates, capture NiII(aryl)(halide) resting state, key C–C NiIII. Oxidative addition NiI, opposed Ni0, rapid NiIII/NiI comproportionation play roles process. The presented herein offer fundamental insight into reactivity broader catalysis.

Language: Английский

Citations

20
Catalysis in the Excited State: Bringing Innate Transition Metal Photochemistry into Play DOI Creative Commons
Fabio Juliá

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4665 - 4680

Published: March 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.

Language: Английский

Citations

4
Ligand-Enabled “Two-in-One” Metallaphotocatalytic Cross Couplings DOI
Jianbin Li, Ding Zhang, Zheng Hu

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1635 - 1654

Published: Jan. 15, 2025

Metallaphotoredox cross coupling (MCC) is ranking among the most advanced synthetic methodology as it can access chemical space that difficult to attain under conventional conditions. Earlier developed MCC mandates an independent transition metal catalyst and respective photocatalyst, thus constituting a dual catalytic manifold. Complementarily, paradigm-shifting metallaphotoredox strategy capitalizes on single photoreactive complex emerging, which brings not only operational simplification but also unexpected mechanistic insights. This perspective compiled recent advances in monocatalytic couplings categorized them based ligands confer distinct photoreactivities various mechanisms. To this end, ligand-enabled oxidative addition, transmetalation, reductive elimination other radical-involving pathways were summarized with notable examples. In way, we wish provide handy guideline for readers who are interested emerging field inspire more future endeavors MCCs beyond.

Language: Английский

Citations

3
Intraligand Charge Transfer Enables Visible‐Light‐Mediated Nickel‐Catalyzed Cross‐Coupling Reactions** DOI Creative Commons
Cristian Cavedon,

Sebastian Gisbertz,

Susanne Reischauer

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(46)

Published: Sept. 26, 2022

We demonstrate that several visible-light-mediated carbon-heteroatom cross-coupling reactions can be carried out using a photoactive NiII precatalyst forms in situ from nickel salt and bipyridine ligand decorated with two carbazole groups (Ni(Czbpy)Cl2 ). The activation of this towards follows hitherto undisclosed mechanism is different previously reported light-responsive complexes undergo metal-to-ligand charge transfer. Theoretical spectroscopic investigations revealed irradiation Ni(Czbpy)Cl2 visible light causes an initial intraligand transfer event triggers productive catalysis. Ligand polymerization affords porous, recyclable organic polymer for heterogeneous catalysis reactions. catalyst shows stable performance packed-bed flow reactor during week continuous operation.

Language: Английский

Citations

46
Poly(heptazine imide) ligand exchange enables remarkable low catalyst loadings in heterogeneous metallaphotocatalysis DOI Creative Commons
Liuzhuang Xing, Qian Yang, Chen Zhu

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: March 17, 2023

Abstract The development of heterogeneous metallaphotocatalysis is great interest for sustainable organic synthesis. rational design and controllable preparation well-defined (site-isolated) metal/photo bifunctional solid catalysts to meet such goal remains a critical challenge. Herein, we demonstrate the incorporation privileged homogeneous bipyridyl-based Ni-catalysts into highly ordered crystalline potassium poly(heptazine imide) (K-PHI). A variety PHI-supported cationic (L n Ni-PHI) have been prepared fully characterized by various techniques including NMR, ICP-OES, XPS, HAADF-STEM XAS. L Ni-PHI exhibit exceptional chemical stability recyclability in diverse C−P, C−S, C−O C−N cross-coupling reactions. proximity cooperativity effects significantly enhances photo/Ni dual catalytic activity, thus resulting low catalyst loadings high turnover numbers.

Language: Английский

Citations

37
Ni‐Catalyzed Photochemical C−N Coupling of Amides with (Hetero)aryl Chlorides DOI

Geyang Song,

Qi Li,

Ding‐Zhan Nong

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(37)

Published: April 17, 2023

This paper reports a photochemical C-N coupling of abundant, but less reactive aryl chlorides, with structurally diverse primary and secondary amides by Ni-mediated without an external photocatalyst. Under the irradiation light (390-395 nm) soluble organic amine as base, reaction allows for successful transformation (hetero)aryl chlorides to wide range N-aryl amides. More than 60 examples are shown, demonstrating feasibility applicability this protocol in synthesis. Mechanic studies indicate that amidation proceeds via Ni(I)-Ni(III) catalytic cycle.

Language: Английский

Citations

25
3D Covalent Organic Frameworks with 16-Connectivity for Photocatalytic C(sp3)–C(sp2) Cross-Coupling DOI
Meng Lu, Shuai‐Bing Zhang, Run‐Han Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(37), P. 25832 - 25840

Published: Sept. 4, 2024

The connectivity (valency) of building blocks for constructing 3D covalent organic frameworks (COFs) has long been limited to 4, 6, 8, and 12. Developing a higher remains great challenge in the field COF structural design. Herein, this work reports hierarchical expansion strategy making 16-connected construct COFs with sqc topology. [16 + 2] construction achieved by condensation between carbazolyl dicyanobenzene-based block (CzTPN) linear diamino linkers (BD or Bpy) affords two (named CzBD CzBpy COF). Furthermore, attributed well-organized donor-acceptor (D-A) heterojunction, Ni chelated (Ni@CzBpy COF) exhibits excellent performance photoredox/Ni dual catalytic C(sp

Language: Английский

Citations

16
Synthesis, Characterization, and Catalytic Activity of Ni(0) (DQ)dtbbpy, an Air-Stable, Bifunctional Red-Light-Sensitive Precatalyst DOI
Jingsheng Li, Pengpeng Wang, Bing Bai

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 5, 2025

Despite a well-established and growing body of work on nickel(0) precatalysts, the potential complexes as bifunctional precatalysts remains underexplored. In this study, we synthesized, characterized, evaluated catalytic activity (Ni(0)(DQ)dtbbpy), bifunctional, red-light-sensitive, air-stable complex. Owing to its unique photophysical properties, it effectively catalyzed etherification amination aryl bromides under 620–630 nm light irradiation, functioning both photocatalyst an active metal catalyst. Mechanistic studies density functional theory (DFT) calculations further confirmed exceptional absorption properties Ni(0)(DQ)dtbbpy in red-light region, well electron transfer process triggered by irradiation.

Language: Английский

Citations

2