A Blueprint for Secondary Coordination Sphere Editing: Approaches Toward Lewis‐Acid Assisted Carbon Dioxide Co‐Activation

ChemSusChem, Год журнала: 2024, Номер 17(13)

Опубликована: Фев. 15, 2024

Abstract Carbon dioxide (CO 2 ) is a potent greenhouse gas of environmental concern. Seeking to offer solution the “CO ‐problem”, chemistry community has turned focus toward transition metal complexes which can activate, reduce, and convert CO into carbon‐based products. The design such systems involves judicious selection both accompanying donor ligand; in part, these efforts are motivated by biological metalloenzymes that undertake similar transformations. As element, metal‐ligand cooperativity, leverages intramolecular interactions between an adjacent secondary ligand site, been acknowledged as vitally important component activation community. These “push‐pull” style where electron density chaperoned onto with electrophile, Lewis‐acid, playing role acceptor. This pairing allows for stabilization reactive C x H y O z ‐containing intermediates bias product selectivity. In laboratory, chemists test hypotheses ideas, enabling rationalization why given metal/Lewis‐acid leads selective reduction outcomes. Concept identifies literature examples highlights key properties, allowing interested contributors design, create, implement novel productive transformations small molecule huge potential impact.

Язык: Английский

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Aluminum in Frustrated Lewis Pair Chemistry

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(34)

Опубликована: Июнь 3, 2024

This review article describes the development of use aluminum compounds in chemistry frustrated Lewis pairs (FLPs) over last 14 years. It also discusses synthesis, reactivity and catalytic applications intermolecular, intramolecular so-called hidden FLPs with phosphorus, nitrogen carbon bases. The intrinsically higher acidity compared to their boron analogs opens up different reaction pathways. results are presented a more or less chronological order. is shown that Al react variety polar non-polar substrates form both stable adducts reversibly activate bonds. Consequently, some title were such as dimerization alkynes, hydrogenation tert-butyl ethylene imines, C-F bond activation, reduction CO

Язык: Английский

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Frustrated Lewis Pair Meets Polyhedral Oligomeric Silsesquioxane: Water-Tolerant Hybrid Porous Networks for Robust, Efficient, and Recyclable CO₂ Catalysis

ACS Applied Materials & Interfaces, Год журнала: 2025, Номер unknown

Опубликована: Янв. 25, 2025

Frustrated Lewis pair chemistry (FLP) occupy a crucial position in nonmetal-mediated catalysis, especially toward activation of inert gas molecules. Yet, one formidable issue homogeneous FLP catalysts is their instability on preservation and recycling. Here we contribute general solution that marries the polyhedral oligomeric silsesquioxane (POSS) with structurally specific frustrated acid to fabricate porous polymer networks, which can form situ water-insensitive heterogeneous upon employing base substrates. The excellent resistance water derives from synergy superhydrophobicity cage multiscale micro/nano-structural effect formed networks. Using CO2 as C1 feedstock, FLP-POSS hybrid materials allow for catalytically conversion variety diamine substrates into medicinal benzimidazole derivatives. Not only units be immobilized networks meeting needs recyclable utilization but, more importantly, are also high catalytic efficiency capable working at near ambient condition owing favorable selectivity. Given this organic/inorganic catalyst features low cost, ease synthesis, little requirements internal structural ordering, it will pave way large-scale preparation amorphous low-cost, robust, sustainable conversion.

Язык: Английский

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Heterogeneous Frustrated Lewis Pair Catalysts: Rational Structure Design and Mechanistic Elucidation Based on Intrinsic Properties of Supports

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Янв. 28, 2025

ConspectusThe discovery of reversible hydrogenation using metal-free phosphoborate species in 2006 marked the official advent frustrated Lewis pair (FLP) chemistry. This breakthrough revolutionized homogeneous catalysis approaches and paved way for innovative catalytic strategies. The unique reactivity FLPs is attributed to base (LB) acid (LA) sites either spatial separation or equilibrium, which actively react with molecules. Since 2010, heterogeneous FLP catalysts have gained increasing attention their ability enhance performance through tailored surface designs improved recyclability, making them promising industrial applications. Over past 5 years, our group has focused on investigating strategically modifying various types solid that are from classic FLPs. We explored systematic characterization techniques unravel underlying mechanisms between active reactants. Additionally, we demonstrated critical role catalysts' intrinsic electronic geometric properties promoting formation stimulating synergistic effects. been greatly enhanced by use advanced such as synchrotron X-ray diffraction, neutron powder photoelectron spectroscopy, extended absorption fine structure, elemental mapping scanning transmission electron microscopy, paramagnetic resonance diffuse-reflectance infrared Fourier transform solid-state nuclear magnetic spectroscopy. These provided deeper insights into structural systems future design catalysts.Understanding distribution overlapping orbitals LA LB pairs essential inducing operando target reallocation external stimuli. For instance, silicoaluminophosphate-type zeolites weak orbital overlap, adsorption polar gas molecules leads heterolytic cleavage Alδ+–Oδ− bond, creating unquenched LA–LB pairs. In a Ru-doped metal–organic framework, Ru–N bond can be polarized metal–ligand charge transfer under light, forming Ru+–N– activation framework represents groundbreaking innovation expands potential existing materials. already employing chemistry dynamically generate products substrates, complete mechanistic interpretation requires thorough examination surrounding environment. hydrogen spillover surfaces improves conversion efficiency suppressing poisoning at metal sites. situ H2–H2O conditions enable production organic chemicals excellent activity selectivity new bifunctional via By highlighting novel featuring induction effects selection elucidate reaction mechanisms, hope this Account will offer strategies designing characterizing research community.

Язык: Английский

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Novel and Highly Efficient Carboxylative Cyclization of CO2 to 2-Oxazolidinones Using Nano-SiO2-Supported Ionic Liquid Sustainable Catalysts

Molecules, Год журнала: 2025, Номер 30(3), С. 633 - 633

Опубликована: Янв. 31, 2025

The conversion of CO2 into 2-oxazolidinones through carboxylative cyclization with propargylic amines is considered an effective method for utilizing waste gas as a sustainable C1 resource and mitigating the greenhouse effect. In this context, series nano-SiO2-supported ionic liquids have been prepared developed multifunctional heterogeneous catalysts in CO2. catalyst IL-SbF6@nano-SiO2 demonstrated high compatibility various amines, achieving excellent yields (90~98%) desired under mild conditions. Additionally, can be easily separated from reaction mixture reused up to six cycles without any significant activity loss. This important chemistry, it reduces potentially lowers costs. study offers novel insights development design green efficient synthesis carbon dioxide.

Язык: Английский

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Anodic reactions matter for cathodic electrocarboxylation with CO2

Chem Catalysis, Год журнала: 2025, Номер unknown, С. 101263 - 101263

Опубликована: Фев. 1, 2025

Язык: Английский

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MOF-Based Frustrated Lewis Pairs: Expanding Horizons in Catalysis

Industrial & Engineering Chemistry Research, Год журнала: 2025, Номер unknown

Опубликована: Фев. 17, 2025

Язык: Английский

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Mechanistic Insights into the Methylation and Formylation of Amines with CO₂: Exploring Diverse CO₂ Activation Models

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 20, 2025

The urgent need to address global warming and resource depletion has spurred research into sustainable methods for the utilization of CO2 as a C1 source. However, challenge remains in developing metal-free, cost-effective, environmentally friendly approaches conversion. Here, we investigate mechanisms activation methylation formylation amines using both theoretical experimental approaches. Our study reveals that process is complex, with "double H model" proving most effective, while reaction more straightforward, favoring "single model." Control experiments confirmed these distinct models by monitoring HCOOH formation. We further evaluated key influencing factors, including Hirshfeld charge nucleophilicity. Based on our findings, successfully designed new reactions, demonstrating practical applications mechanisms. This provides valuable insights conversion strategies, advancing field chemistry.

Язык: Английский

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Using Gas Molecules to Assemble Value‐Added Materials through Dynamic Gas‐Bridged Bond

Macromolecular Rapid Communications, Год журнала: 2025, Номер unknown

Опубликована: Фев. 22, 2025

Abstract The conversion and utilization of greenhouse gases other polluting in a green way represents crucial strategy for developing C 1 chemistry mitigating the dual crises energy scarcity effect. As class polyatomic molecules with relatively simple structure, gas are directly involved assembled process as building blocks, converting them into polymer assemblies under mild low consumption, constructing recyclable functional materials, which is great significance to enrich block assembly promote sustainable value‐added gas. dynamic bridge new combining molecules, it provides possibility assembly. This perspective systematically introduces formation mechanism unique physicochemical properties bridge, discusses latest research progress gas‐bridged particular focus on three key aspects: gas‐regulated system, gas‐constructed efficient catalysis. Finally, critical challenges future directions materials based also highlighted.

Язык: Английский

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Lithium Anionic Dicarbenes or Acetylides: What is in the Name?

Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown

Опубликована: Март 11, 2025

Abstract The two‐fold deprotonation of the C2‐arylated 1,3‐imidazolium salts (IPr‐Ar)X ( 1 ‐Ar)X (IPr‐Ar = ArC{N(Dipp)CH} 2 ; Ar Ph, 4‐Me NC 6 H 4 (DMP) or 4‐PhC (Bp); Dipp 2,6‐ i Pr C 3 ) with n BuLi affords so‐called anionic dicarbenes Li(ADC) ‐Ar) (ADC ArC{N(Dipp)C} ). ‐Ar can be used to prepare a variety main group heterocycles, however their structures in solid‐state remained hitherto unknown. Herein reported single‐crystal X‐ray diffraction studies reveal an acetylide type [ArC{N(Dipp)}(Dipp)NC≡CLi)] dimeric 2) trimeric 3) molecular structure for ‐Ar. Treatment ‐Ph Et B cleanly yields monoanionic carbene Li[(ADC)(BEt )] ‐Ph) featuring weakly coordinating anion embedded same entity. readily undergo reactions CO and N O form ring‐closing products Li[(ADC)(CO ] 5 Li[(ADC)N O] ‐Ar), respectively.

Язык: Английский

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