Anionic or Radical Polymerization Catalyzed by Metal Triflate-Based Lewis Pairs: A Comprehensive Mechanistic Study DOI

Riki Akita,

Mayo Horibe,

Katsuhiro Yamamoto

et al.

Macromolecules, Journal Year: 2024, Volume and Issue: 57(10), P. 4926 - 4936

Published: May 15, 2024

Ester and amide enolates are important propagating species in organometallic-mediated polymerization of polar vinyl monomers, but the effects transition main group metallic counterions have not been systematically understood. In this study, various metal triflates along with PPh3 used to catalyze Lewis pair anionic (LPAP) or radical (LPRP) (meth)acrylates acrylamides, elements solvents determine dominant propagation mechanism. Specifically, LPAP LPRP proceed using early late triflates, respectively, organic on-water. The elementary reactions PPh3/Fe(OTf)3 kinetically investigated. Notably, follows pseudo-second-order kinetics respect monomer concentration, which contributes initiation propagation, whereas PPh3/Sc(OTf)3 proceeds pseudo-zero-order kinetics. This indicates that react unactivated free Sc-activated LPAP. study demonstrates triflate-based pairs can generate new polymerizable distinctive reactivities.

Language: Английский

Defect-Induced Synergetic Effect of Bi-Based Compounds for One-Pot Conversion of Organic Pollutants into CO via Coupling Photodegradation of Carbamazepine with Photoreduction of CO2 DOI
Lingling Zheng, Lei Tian,

Longshuai Zhang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2134 - 2143

Published: Jan. 25, 2024

The waste of carbon sources and greenhouse gas production during wastewater treatment have become extremely important environmental issues. Herein, the BiOBr/BiVO4 compounds with defect-induced frustrated Lewis acid–base pairs (DFLPs) internal charge transfer were fabricated to convert organic pollutants into CO nearly 100% selectivity. oxygen vacancy (Ov) induced built-in electric field in create directional from BiOBr BiVO4. Density functional theory (DFT) calculations prove that Ov combines its adjacent hydroxyls form DFLP active sites can additionally capture activate CO2. Meanwhile, reduce formation-free energy COOH* intermediates, which is key rate-limiting step CO2 high This system has achieved selective conversion value-added chemicals pollutant degradation provides a theoretical basis for actual recycling sources.

Language: Английский

Citations

31
A review of frustrated Lewis pair enabled monoselective C–F bond activation DOI Creative Commons
Kenneth Lye, Rowan D. Young

Chemical Science, Journal Year: 2024, Volume and Issue: 15(8), P. 2712 - 2724

Published: Jan. 1, 2024

Frustrated Lewis pair (FLP) bond activation chemistry has greatly developed over the last two decades since seminal report of metal-free reversible hydrogen activation. Recently, FLP systems have been utilized to allow monoselective C-F (at equivalent sites) in polyfluoroalkanes. The problem 'over-defluorination' functionalization polyfluoroalkanes (where multiple fluoro-positions are uncontrollably functionalized) a long-standing chemical fluorocarbon for 80 years. mediated is complementary other solutions address and offers several advantages unique opportunities. This perspective highlights some these opportunities places development into context wider effort overcome 'over-defluorination'.

Language: Английский

Citations

20
Frustrated Radical Pairs in Organic Synthesis DOI
Minsoo Ju, Zhipeng Lu, Luiz F. T. Novaes

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(36), P. 19478 - 19489

Published: Sept. 1, 2023

Frustrated radical pairs (FRPs) describe the phenomenon that two distinct radicals─which would otherwise annihilate each other to form a closed-shell covalent adduct─can coexist in solution, owing steric repulsion or weak bonding association. FRPs are typically formed via spontaneous single-electron transfer between sterically encumbered precursors─an oxidant and reductant─under ambient conditions. The components of FRP exhibit orthogonal chemical properties can often act cooperativity achieve interesting reactivities. Initially observed study traditional frustrated Lewis pairs, have recently been shown be capable homolytically activating various bonds. In this Perspective, we will discuss discovery FRPs, their fundamental reactivity bond activation, recent developments use synthetic organic chemistry, including C–H functionalization. We anticipate provide new reaction strategies for solving challenging problems modern synthesis.

Language: Английский

Citations

32
Advances in CO2 activation by frustrated Lewis pairs: from stoichiometric to catalytic reactions DOI Creative Commons
Md. Nasim Khan, Yara van Ingen,

Tribani Boruah

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(47), P. 13661 - 13695

Published: Jan. 1, 2023

Frustrated Lewis pair systems have been explored efficiently in homogeneous and heterogeneous conditions for the activation reduction of CO 2 to various useful products stoichiometric as well catalytic reactions.

Language: Английский

Citations

32
Metal‐Free Catalytic Formation of a Donor‐Acceptor‐Donor Molecule and Its Lewis Acid‐Adduct Singlet Diradical with High‐Efficient NIR‐II Photothermal Conversion DOI

Shanshan Kong,

Li‐Ming Yang,

Quanchun Sun

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(19)

Published: March 5, 2024

Abstract We have synthesized a quinone‐incorporated bistriarylamine donor‐acceptor‐donor (D–A–D) semiconductor 1 by B(C 6 F 5 ) 3 (BCF) catalyzed C−H/C−H cross coupling via radical ion pair intermediates. Coordination of Lewis acids BCF and Al(OR (R =C(CF to the afforded diradical zwitterions 2 integer electron transfer. Upon binding acids, LUMO energy is significantly lowered band gap narrowed from 1.93 eV ( 1.01 1.06 ). are rare near‐infrared (NIR) dyes with broad absorption both centered around 1500 nm. By introducing photo generator, can be generated light‐dependent control. Furthermore, transfer process also reversibly regulated addition CH CN. In addition, temperature sharply increased reached as high 110 °C in 10 s upon irradiation near‐infrared‐II (NIR‐II) laser (1064 nm, 0.7 W cm −2 ), exhibiting fast response laser. It displays excellent photothermal stability (PT) conversion efficiency 62.26 % high‐quality PT imaging.

Language: Английский

Citations

8
Recent Advances on C—H Functionalization via Oxidative Electrophotocatalysis DOI

Aman Hasil,

Rui Chang,

Juntao Ye

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(3), P. 728 - 728

Published: Jan. 1, 2024

Language: Английский

Citations

8
B(C6F5)3-catalyzed selective C–H chalcogenation of arenes and heteroarenes DOI Creative Commons
Milan Pramanik,

Sampurna Das,

Rasool Babaahmadi

et al.

Chem, Journal Year: 2024, Volume and Issue: 10(9), P. 2901 - 2915

Published: June 27, 2024

The synthesis of organochalcogenides remains a valuable area research due to their widespread biological applications, particularly in pharmaceuticals. Herein, our study details the B(C6F5)3-catalyzed Csp2–H functionalization diverse arenes, heteroarenes, and pharmacophores with thiosuccinimides or selenosuccinimides, providing selective access chalcogenated products. This protocol enables late-stage chalcogenation drug molecules such as anti-inflammatory naproxen, estrogen steroid hormone estradiol derivatives, industrially relevant trifluoromethylthiolation reaction. Furthermore, this C–S coupling methodology provides facile metal-free route synthesize vortioxetine, an antidepressant drug, plethora significant organic motifs. Detailed NMR, EPR analyses, density functional theory (DFT) computational studies indicate that elongation thiosuccinimide N–S bond is assisted by boron-centered adduct, which then leads stable ion pair arene. analysis shows transient radical pair, potentially off-cycle species, not directly involved catalytic process.

Language: Английский

Citations

6
Heterolytic H2 Activation in Heterogeneous Hydrogenation/Hydroprocessing Catalysis DOI
Tae Wan Kim, Dong-Un Kim, Soo Hyun Kim

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(8)

Published: Jan. 5, 2024

Abstract In heterogeneous catalysis, heterolytic H 2 activation for (selective) hydrogenation and hydroprocessing reactions involves the dissociation of adsorbed molecules into proton (H δ+ ) hydride δ− on catalyst surface. This approach offers several advantages, including high selectivity polar bond (s), a low energy barrier dissociation, capacity reaction‐favorable adsorption, reduced poisoning. requires construction frustrated Lewis pairs surface, satisfying specific criteria, such as having an abundant quantity with steric hindrance maintaining certain distance 3–5 Å between pairs. review highlights intrinsic properties based state‐of‐the‐art reports. The main components necessary this include supports strong basic sites and/or oxygen vacancies, metals single atom. For purpose, designed catalytic materials aim to strengthen acidity basicity, improve polarization pairs, enrich maximize interfacial area metal species base, enhance metal–support interaction. Therefore, catalysts retaining characteristics will be significantly effective in various reactions.

Language: Английский

Citations

5
Mechanistic studies on single-electron transfer in frustrated Lewis pairs and its application to main-group chemistry DOI Creative Commons
Lars J. C. van der Zee, J. Hofman, Joost M. van Gaalen

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(10), P. 4862 - 4876

Published: Jan. 1, 2024

Here, we discuss predicting thermal and photoinduced single-electron transfer (SET) in frustrated Lewis pairs (FLPs) characterizing the resulting radical pair. We then extend these methods' application to main-group chemistry.

Language: Английский

Citations

5
Single electron reduction of NHC–CO2–borane compounds DOI Creative Commons
Agustín Morales, Caroline Gonçalves, Alix Sournia‐Saquet

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(9), P. 3165 - 3173

Published: Jan. 1, 2024

NHC–CO 2 –borane compounds were shown to be reduced by one electron at a reduction potential as mild −1.34 V vs. Fc +/0 . The resulting radical anion was crystallographically characterised and showed reactivity similar that of the CO anion.

Language: Английский

Citations

4