Low oxidation state and hydrido group 2 complexes: synthesis and applications in the activation of gaseous substrates

Chemical Society Reviews, Год журнала: 2024, Номер 53(10), С. 5054 - 5082

Опубликована: Янв. 1, 2024

This review summarises advances in the chemistry of low-oxidation state and hydrido group 2 metal complexes, focussing on their use for reductive activation feed-stock gaseous small molecules, subsequent transformation into value added products.

Язык: Английский

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Accelerating materials property prediction via a hybrid Transformer Graph framework that leverages four body interactions

npj Computational Materials, Год журнала: 2025, Номер 11(1)

Опубликована: Янв. 18, 2025

Machine learning has advanced the rapid prediction of inorganic materials properties, yet data scarcity for specific properties and capturing thermodynamic stability remains challenging. We propose a framework utilizing Graph Neural Network with composition-based crystal structure-based architectures, combined transfer scheme. This approach accurately predicts energy-related (e.g., total energy, energy above convex hull, band gap) data-scarce mechanical bulk shear modulus). Our model incorporates four-body interactions, periodicity structural characteristics. It outperforms state-of-the-art models in 8 property regression tasks. Also, this local atomic environments global features better than several models. Transfer addresses scarcity, while separate architecture analysis allows application to lacking structure information. framework's interpretability aids understanding elemental contributions, enhancing material design discovery. Continuous advancements promise further performance improvements, driving efficient accurate prediction.

Язык: Английский

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Palladium-Catalyzed Carbonylations: Application in Complex Natural Product Total Synthesis and Recent Developments

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(8), С. 4925 - 4941

Опубликована: Янв. 27, 2023

Carbon monoxide is a cheap and abundant C1 building block that can be readily incorporated into organic molecules to rapidly build structural complexity. In this Perspective, we outline several recent (since 2015) examples of palladium-catalyzed carbonylations in streamlining complex natural product total synthesis highlight the strategic importance these carbonylation reactions corresponding synthesis. The selected include spinosyn A, callyspongiolide, perseanol, schizozygane alkaloids, cephanolides, bisdehydroneostemoninine related stemona alkaloids. We also provide our perspective about advancements future developments carbonylations.

Язык: Английский

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Applications of low-valent compounds with heavy group-14 elements

Chemical Society Reviews, Год журнала: 2024, Номер 53(12), С. 6150 - 6243

Опубликована: Янв. 1, 2024

We have compiled the recent progress of low-valent group-14 compounds in catalysis, polymerization, small molecule activation, thin film deposition, photophysical properties, and medicinal properties.

Язык: Английский

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Ligand Exchange at Carbon: Synthetic Entry to Elusive Species and Versatile Reagents

JACS Au, Год журнала: 2024, Номер 4(5), С. 1709 - 1722

Опубликована: Апрель 15, 2024

How different is carbon compared to other elements in the periodic table? Can compounds be regarded as coordination complexes with central element undergoing a facile exchange of its ligands? Although clearly plays special role among table, recent studies have drawn parallels between bonding situation and reactivity transition metal complexes. This Perspective summarizes reports about ylidic zwitterionic that were shown exhibit ambiguous situations can interpreted donor–acceptor interactions similar bond neutral ligand. Based on this conception, ligand reactions prototypical realized at atoms, enabling new synthetic strategies for synthesis reactive species building blocks. In particular, N2, CO, phosphine ligands led development mild method accessing reagents unusual properties, such vinylidene ketenes or stable ketenyl anions, open up diverse but still poorly explored follow-up chemistry.

Язык: Английский

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Synergizing Mo_n Clusters and Mo₂C Nanoparticles on Oxidized Carbon Nanotubes Boosting the CO₂ Reduction Activity

ACS Catalysis, Год журнала: 2024, Номер 14(14), С. 10939 - 10950

Опубликована: Июль 5, 2024

The design and synthesis of highly efficient selective catalysts for CO2 thermal reduction remain a challenging issue modern catalysis. Molybdenum carbide has attracted great interest in CO2-to-CO conversion (Reverse Water Gas Shift process, RWGS) because its ability to dissociate H2. However, single dominant Mo- or C-terminated facets molybdenum are unlikely activate H2 molecules simultaneously. Herein, we demonstrate how structural diversity cogenerated species (i.e., Mon nanoclusters Mo2C nanoparticles) on the surface an oxygen-enriched C-carrier boosts synergistically chemoselective RWGS process with rates up 581 μmolCO2·gMo–1·s–1 CO selectivity > 99% already at 400 °C under H2-rich environment. This catalytic outcome ranks among highest reported so far carbide- noble metal-based it is 1.8 times higher than that measured Mo2C-based nanoparticles. enhanced reactivity structurally mixed catalyst been ascribed synergistic modulation geometrical electronic structure different Mo sites reduces temperature which production starts facilitates desorption pathway. Experimental silico studies have also unveiled existence linear correlation between percentage high-valence metal active-phase composition (Moδ+ %) increase rate.

Язык: Английский

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Heterogeneous catalysis for the environment

The Innovation Materials, Год журнала: 2024, Номер unknown, С. 100090 - 100090

Опубликована: Янв. 1, 2024

<p>Anthropogenic climate and environmental changes increasingly threaten the sustainability of life on Earth, hindering sustainable development human societies. These detrimental ecological are driven by activities that have elevated atmospheric levels greenhouse gases toxic substances, increased inorganic organic pollutants in water bodies, led to accumulation solid waste soils. Over next two three decades, impacts change, pollution, soil contamination expected intensify, posing increasing risks health global stability. Considering these trends, it is essential implement robust mitigation adaptation strategies. This paper analyzes pollution problems from perspectives atmospheric, water, contamination. It summarizes current research heterogeneous catalysis for treating gaseous, liquid, phases, with an emphasis key challenges applying catalytic conversion technologies cost-effective industrial settings. Finally, strategies mitigating via discussed material flow, energy data flow. aims offer scientific insights enhance future practice remediation.</p>

Язык: Английский

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Coordination and Homologation of CO at Al(I): Mechanism and Chain Growth, Branching, Isomerization, and Reduction

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(28), С. 12942 - 12953

Опубликована: Июль 5, 2022

Homologation of carbon monoxide is central to the heterogeneous Fischer-Tropsch process for production hydrocarbon fuels. C-C bond formation has been modeled by homogeneous systems, with [C

Язык: Английский

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The Cyanoketenyl Anion [NC₃O]⁻

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(20)

Опубликована: Март 12, 2024

Abstract Cumulenes and heterocumulenes with three or more cumulative multiple bonds are usually reactive species that serve as valuable building blocks for complex molecules but tend to isomerize cyclize therefore difficult isolate. Using a mild ligand exchange reaction at the carbon in α‐metalated ylides, we have now succeeded synthesis gram‐scale isolation of elusive cyanoketenyl anion [NC 3 O] − . Despite its assumed cumulene‐like structure delocalization negative charge across whole 5‐atom molecule, it features bent geometry nucleophilic central atom. Computational studies reveal an ambiguous bonding situation anion, which can be illustrated only by combination different resonance structures. Nonetheless, remarkable stability, thus allowing storage potassium‐crown ether salt application highly functional synthetic block. The readily reacts series small form organic compounds, including industrially compounds such cyanoacetate. This work demonstrated generated novel methods open up atom‐economic pathways from abundant molecules.

Язык: Английский

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One pot conversion of phenols and anilines to aldehydes and ketones exploiting α gem boryl carbanions

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Май 7, 2024

Abstract Functional group interconversion is an important asset in organic synthesis. Phenols/anilines being naturally abundant and the carbonyl most common a wide range of bioactive molecules, efficient conversion prime interest. The reported methods require transition metal catalyzed cross coupling which limits its applicability. Here we have described method for synthesizing various aldehydes ketones, starting from phenol protected anilines via Csp 2 -O/N bond cleavage one-pot/stepwise manner. Our synthetic found to be compatible with diverse phenols carrying sensitive functional groups including halides, esters, ketal, hydroxyl, alkenes, terminal alkynes as well substitution on aryl cores. A short-step synthesis molecules their functionalization been executed. Starting BINOL, photocatalyst has designed. Here, developed metal-free protocol ketones.

Язык: Английский

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