The chemistry of heterocycles in the 21st century

Russian Chemical Reviews, Год журнала: 2024, Номер 93(7), С. RCR5125 - RCR5125

Опубликована: Июль 1, 2024

The chemistry of heterocyclic compounds has traditionally been and remains a bright area chemical science in Russia. This is due to the fact that many heterocycles find widest application. These are key structural fragments most drugs, plant protection agents. Many natural also derivatives heterocycles. At present, more than half hundreds millions known collective review devoted achievements Russian chemists this field over last 15–20 years. presents leading heterocyclists representing both RAS institutes university science. It worth noting wide scope review, terms geography author teams, covering whole our large country, diversity research areas. Practically all major types represented review. special attention focused on practical applications design new drugs biologically active compounds, high-energy molecules, materials for organic electronics photovoltaics, ligands coordination chemistry, other rapidly developing advances would not be possible without development fundamental transformations chemistry.<br> Bibliography — 2237 references.

Язык: Английский

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Switching Electrocatalytic Hydrogen Evolution Pathways through Electronic Tuning of Copper Porphyrins

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(13)

Опубликована: Фев. 7, 2024

The electronic structure of metal complexes plays key roles in determining their catalytic features. However, controlling structures to regulate reaction mechanisms is fundamental interest but has been rarely presented. Herein, we report tuning Cu porphyrins switch pathways the hydrogen evolution (HER). Through controllable and regioselective β-oxidation porphyrin 1, synthesized analogues 2-4 with one or two β-lactone groups either a cis trans configuration. Complexes 1-4 have same Cu-N

Язык: Английский

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Ligand-Bound CO₂ as a Nonclassical Route toward Efficient Photocatalytic CO₂ Reduction with a Ni N-Confused Porphyrin

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(15), С. 10550 - 10558

Опубликована: Апрель 8, 2024

Implementing the synergistic effects between metal and ligand has successfully streamlined energetics for CO2 activation gained high catalytic activities, establishing important breakthroughs in photocatalytic reduction. Herein, we describe a Ni(II) N-confused porphyrin complex (NiNCP) featuring an acidic N–H group. It is readily deprotonated exists anion form during catalysis. Owing to this functional site, NiNCP gave rise outstanding turnover number (TON) as 217,000 with 98% selectivity reduction CO, while parent (NiTPP) was found be nearly inactive. Our mechanistic analysis revealed nonclassical reaction pattern where effectively activated via attack of Lewis-basic ligand. The resulting ligand-bound adduct could further reduced produce CO. This new metal–ligand effect anticipated inspire design highly active catalysts small molecule activations.

Язык: Английский

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Understanding the Interplay of the Brønsted Acidity of Catalyst Ancillary Groups and the Solution Components in Iron-porphyrin-Mediated Carbon Dioxide Reduction

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(6), С. 3721 - 3731

Опубликована: Фев. 2, 2024

The rapid and efficient conversion of carbon dioxide (CO2) to monoxide (CO) is an ongoing challenge. Catalysts based on iron-porphyrin cores have emerged as excellent electrochemical mediators the two proton + electron reduction CO2 CO, many design features that promote function are known. Of those features, incorporation Brønsted acids in second coordination sphere iron ion has a significant impact catalyst turnover kinetics. often form hydroxyphenyl groups. Herein, we explore how acidity ancillary 2-hydroxyphenyl group affects performance electrocatalysts. A series meso-5,10,15,20-tetraaryl porphyrins were prepared where only functional at 5-meso position ionizable proton. cyclic voltammetry (CV) experiments reveal complex with −OMe positioned para −OH shows largest rate constants acetonitrile solvent. This least acidic compounds surveyed. frequency derivative can be further improved addition 4-trifluoromethylphenol solution. In contrast, −CF3 opposite smallest constants, its less enhanced phenols reaction solutions. origin this effect rationalized kinetic isotope density calculations. We conclude catalysts weaker internal coupled stronger external acid additives provide superior

Язык: Английский

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Enzymatic and Bioinspired Systems for Hydrogen Production

International Journal of Molecular Sciences, Год журнала: 2023, Номер 24(10), С. 8605 - 8605

Опубликована: Май 11, 2023

The extraordinary potential of hydrogen as a clean and sustainable fuel has sparked the interest scientific community to find environmentally friendly methods for its production. Biological catalysts are most attractive solution, they usually operate under mild conditions do not produce carbon-containing byproducts. Hydrogenases promote reversible proton reduction in variety anoxic bacteria algae, displaying unparallel catalytic performances. Attempts use these sophisticated enzymes scalable production have been hampered by limitations associated with their stability. Inspired nature, significant efforts made development artificial systems able evolution reaction, via either electrochemical or light-driven catalysis. Starting from small-molecule coordination compounds, peptide- protein-based architectures constructed around center aim reproducing hydrogenase function into robust, efficient, cost-effective catalysts. In this review, we first provide an overview structural functional properties hydrogenases, along integration devices energy Then, describe recent advances homogeneous envisioned mimic hydrogenases.

Язык: Английский

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Coordination-driven electrocatalysts as an evolving wave of enthusiasm for sustainable hydrogen production

Coordination Chemistry Reviews, Год журнала: 2023, Номер 500, С. 215496 - 215496

Опубликована: Ноя. 6, 2023

Язык: Английский

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Protic ionic liquids for sustainable uses

Green Chemistry, Год журнала: 2023, Номер 26(3), С. 1092 - 1131

Опубликована: Дек. 8, 2023

This review provides an overview of the current state-of-the-art and major trends in application protic ionic liquids (PILs) to sustainable chemistry.

Язык: Английский

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Synthesis and Characterization of [Ni(H₂O)(7-P^Ph₂N^ArSO3)₂](NaBF₄) for Light-Driven Quantum Dot-Catalyst Hydrogen Evolution

Energy & Fuels, Год журнала: 2025, Номер unknown

Опубликована: Янв. 14, 2025

Light-driven hydrogen generation from water is a route to carbon-neutral fuels. However, the integrated light absorbers and catalysts must be compatible functional under same conditions. A sulfate-functionalized complex, [Ni(H2O)(7-PPh2NArSO3)2](NaBF4), where PPh2NArSO3 = 4-(3,6-diphenyl-1,3,6-azadiphosphepan-1-yl)benzenesulfonate), was synthesized characterized. solid-state structure single-crystal X-ray crystallography also reported. The electrocatalytic activity for evolution of this complex in 7:3 H2O:CH3CN characterized by cyclic voltammetry controlled potential electrolysis, with maximum observed rate 83 s–1. Density theory used characterize favorable binding sulfate functionalities cadmium sulfide quantum dots. Experimental assembly these onto dots successful. Both fast electron transfer light-driven pH-dependent were observed.

Язык: Английский

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Bioinspired Catalyst Design Principles: Progress in Emulating Properties of Enzymes in Synthetic Catalysts

ACS Catalysis, Год журнала: 2023, Номер 13(18), С. 11883 - 11901

Опубликована: Авг. 25, 2023

Catalysis enables many aspects of modern life, including fuels, products, plastics, and medicines. Recent advances in catalysis have enabled us to realize higher efficiencies new processes. Ideally, we seek achieve high rates selective conversions using catalysts derived from abundantly available elements operating under mild conditions, specifically lower reaction temperatures pressures. Such could enable decentralized, on-demand synthesis chemicals energy carriers. Nature has demonstrated the feasibility this approach with enzymes, which showcase catalytic processes at low pressures nonprecious metals. Current thinking holds that addition active site, complexity enzyme structure, protein scaffold, is also critical achieving performance. Recreating environment been a long-standing scientific goal. However, still understand functions enzymes better than de novo design mimic features, while retaining their activity selectivity more demanding conditions. In Perspective, will critically examine four key areas catalyst incorporate chemical structural properties into synthetic catalysts: (i) use confinement enhance activity, (ii) tailoring around (iii) proton transport, (iv) bifunctionality cooperativity.

Язык: Английский

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Proton transfer kinetics of transition metal hydride complexes and implications for fuel-forming reactions

Chemical Society Reviews, Год журнала: 2023, Номер 52(20), С. 7137 - 7169

Опубликована: Янв. 1, 2023

This review discusses proton transfer kinetics for reactions involving transition metal hydride complexes, highlighting the techniques used to measure rate constants and implications fuel-forming reactions.

Язык: Английский

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