Metal-Free Heterogeneous Asymmetric Hydrogenation of Olefins Promoted by Chiral Frustrated Lewis Pair Framework DOI
Yin Zhang, Jun Guo,

Peter VanNatta

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 146(1), P. 979 - 987

Published: Dec. 20, 2023

The development of metal-free and recyclable catalysts for significant yet challenging transformations naturally abundant feedstocks has long been sought after. In this work, we contribute a general strategy combining the rationally designed crystalline covalent organic framework (COF) with newly developed chiral frustrated Lewis pair (CFLP) to afford (CFLPF), which can efficiently promote asymmetric olefin hydrogenation in heterogeneous manner, outperforming homogeneous CFLP counterpart. Notably, CFLPF exhibits superior activity/enantioselectivity addition excellent stability/recyclability. A series situ spectroscopic studies, kinetic isotope effect measurements, density-functional theory computational calculations were also performed gain an insightful understanding catalysis performances CFLPF. Our work not only increases versatility but broadens reactivity porous materials (FLP) chemistry, thereby suggesting new approach practical substantial through advancement novel from both concept design perspectives.

Language: Английский

Carbon Monoxide in Main-Group Chemistry DOI
Shiori Fujimori, Shigeyoshi Inoue

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(5), P. 2034 - 2050

Published: Jan. 24, 2022

The usage of carbon monoxide (CO) as a C1 feedstock for carbonylation has been an important subject numerous studies over century. chemistry in this field evolved significantly, and several processes (e.g., Fischer-Tropsch, Monsanto, Cativa process) have even industrialized to serve humankind our daily lives. CO is also crucial ligand (carbonyl) organometallic chemistry, transition-metal carbonyl complexes widely used homogeneous catalysts various chemical transformations. Historically, carbonyls considered be dominant these purposes. In recent decades, main-group elements, especially naturally abundant elements the Earth's crust such silicon aluminum, gained much attention, they are eco-friendly low toxicity compared late transition metals. Recent developments revealed reactivity which can mimic that toward small molecules H2, alkenes, alkynes, along with monoxide. This Perspective highlights activation by compounds leads formation or insertion into element center well reductive homologation CO.

Language: Английский

Citations

110
Adsorption and activation, active site and reaction pathway of photocatalytic CO2 reduction: A review DOI
Yong‐Xing He, Lin Yin,

Niannian Yuan

et al.

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 481, P. 148754 - 148754

Published: Jan. 14, 2024

Language: Английский

Citations

77
Unveiling the Synergistic Role of Frustrated Lewis Pairs in Carbon‐Encapsulated Ni/NiOx Photothermal Cocatalyst for Enhanced Photocatalytic Hydrogen Production DOI Creative Commons
Zhi Yang, Taiyu Huang,

Meng Li

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(24)

Published: March 10, 2024

Abstract The development of high‐density and closely spaced frustrated Lewis pairs (FLPs) is crucial for enhancing catalyst activity accelerating reaction rates. However, constructing efficient FLPs by breaking classical bonds poses a significant challenge. Here, this work has made pivotal discovery regarding the Jahn–Teller effect during formation grain boundaries in carbon‐encapsulated Ni/NiOx (Ni/NiO x @C). This facilitates O (V ) Ni vacancy sites with different charge polarities, specifically FLP‐V ‐C basic acidic sites. synergistic interaction between not only reduces energy barriers water adsorption splitting, but also induces strong photothermal effect. mutually reinforcing contributes to exceptional performance Ni/NiO @C as cocatalyst photothermal‐assisted photocatalytic hydrogen production. Notably, @C/g‐C 3 N 4 (NOCC) composite photocatalyst exhibits remarkable production rate 10.7 mmol g −1 h , surpassing that Pt 1.76 times. Moreover, NOCC achieves an impressive apparent quantum yield 40.78% at wavelength 380 nm. paves way designing novel defect‐state multiphase cocatalysts adjacent FLP sites, which hold promise various catalytic reactions.

Language: Английский

Citations

32
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
The Impact of Boron Hybridisation on Photocatalytic Processes DOI Creative Commons

Alessandro Marotta,

Callum E. Adams,

John J. Molloy

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(38)

Published: June 24, 2022

Recently the fruitful merger of organoboron chemistry and photocatalysis has come to forefront organic synthesis, resulting in development new technologies access complex (non)borylated frameworks. Central success this combination is control boron hybridisation. Contingent on photoactivation mode, as its neutral planar form or tetrahedral boronate can be used regulate reactivity. This Minireview highlights current state art photocatalytic processes utilising compounds, paying particular attention role hybridisation for target transformation.

Language: Английский

Citations

57
Porous frustrated Lewis pair catalysts: Advances and perspective DOI Creative Commons
Yin Zhang, Pui Ching Lan,

Kyle Martin

et al.

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(3), P. 439 - 457

Published: Jan. 18, 2022

Language: Английский

Citations

51
Chiral Frustrated Lewis Pair@Metal‐Organic Framework as a New Platform for Heterogeneous Asymmetric Hydrogenation DOI
Yin Zhang, Songbo Chen, Abdullah M. Al‐Enizi

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(2)

Published: Nov. 9, 2022

Asymmetric hydrogenation, a seminal strategy for the synthesis of chiral molecules, remains largely unmet in terms activation by non-metal sites heterogeneous catalysts. Herein, as demonstrated combined computational and experimental studies, we present general integrating rationally designed molecular frustrated Lewis pair (CFLP) with porous metal-organic framework (MOF) to construct catalyst CFLP@MOF that can efficiently promote asymmetric hydrogenation manner, which first time extends concept from homogeneous system catalysis. Significantly, developed CFLP@MOF, inherits merits both catalysts, high activity/enantio-selectivity excellent recyclability/regenerability. Our work not only advances new platform but also opens avenue design preparation advanced catalysts

Language: Английский

Citations

43
Recent advances in borenium catalysis DOI
Xinyue Tan, Huadong Wang

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(7), P. 2583 - 2600

Published: Jan. 1, 2022

Borenium ions are strong Lewis acids because of the positive charge on boron. While their high reactivity had long restricted role in organic synthesis to stoichiometric reagents, past ten years introduction suitable supporting ligands, such as N-heterocyclic carbenes, has enabled them function competent catalysts for various transformations involving activation covalent bonds, H-H, Si-H, B-H, C-H and C-C bonds. This review provides an overview recent advances borenium-catalysed reactions with emphasis catalyst synthesis, methodology development mechanistic insight.

Language: Английский

Citations

42
Engineering Nanostructured Interfaces of Hexagonal Boron Nitride-Based Materials for Enhanced Catalysis DOI
Hao Chen, De‐en Jiang, Zhenzhen Yang

et al.

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 56(1), P. 52 - 65

Published: Nov. 15, 2022

ConspectusHexagonal boron nitrides (h-BNs) are attractive two-dimensional (2D) nanomaterials that consist of alternating B and N atoms layered honeycomb-like structures similar to graphene. They have exhibited unique properties promising application potentials in the field energy storage transformation. Recent advances utilizing h-BN as a metal-free catalyst oxidative dehydrogenation propane triggered broad interests exploring catalysis. However, h-BN-based materials robust nanocatalysts heterogeneous catalysis still underexplored because limited methodologies capable affording with controllable crystallinity, abundant porosity, high purity, defect engineering, which played important roles tuning their catalytic performance. In this Account, our recent progress addressing above issues will be highlighted, including synthesis high-quality via both bottom-up top-down pathways utilization catalysts or supports tune interfacial electronic on metal nanoparticles (NPs). First, we focus large-scale fabrication nanosheets (h-BNNSs) improved surface area, satisfactory tunable defects. derived from traditional approaches using trioxide urea starting generally contains carbon/oxygen impurities has low crystallinity. Several new strategies were developed address issues. Using bulk precursor gas exfoliation liquid nitrogen, single- few-layered h-BNNS defects could generated. Amorphous precursors converted crystallinity assisted by magnesium metallic flux successive dissolution/precipitation/crystallization procedure. The as-fabricated featured purity well porosity. An ionothermal metathesis procedure was inorganic molten salts (NaNH2 NaBH4) precursors. scaffolds produced large scale yield, as-afforded possessed Second, as-prepared library hydrogenation reactions summarized, they enhanced activity over counterparts previous method. Third, interface modulation between NPs defects' support highlighted. strong metal-support interaction (SMSI) constructed without involving reducible oxides deploying specific salts, acting CO oxidation. Under conditions simulated for practical exhaust systems, efficiency together thermal stability sintering resistance achieved. Across all these examples, insights into structures, defects, interfaces emerge in-depth characterization through microscopy, spectroscopy, diffraction

Language: Английский

Citations

41
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

33