Nanoarchitectonics of Non-Noble-Metal-Based Heterogeneous Catalysts for Transfer Hydrogenation Reactions: Detailed Insights on Different Hydrogen Sources

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 4211 - 4248

Published: March 5, 2024

Catalytic transfer hydrogenation (CTH) methodology has drawn profound attention of researchers as an economical and environmentally benign alternate to conventional method. Unlike method, CTH exhibits better reaction efficiency atom economy, it makes use simple, easily accessible, low-cost hydrogen sources. Current research on reactions is oriented toward the development non-noble-metal-based catalysts due their high abundance potential large-scale applicability. In this Review, different organic transformation reactions, such nitroarenes, nitriles, alkenes, alkynes, carbonyl compounds, hydrogenolysis, reductive amination, formylation using sources have been summarized comprehensively. addition, synthesis strategies heterogeneous structure–activity relationship involving metal–support interaction, single-atom catalysis, synergistic effect are highlighted. Furthermore, optimization parameters─such temperature, time, solvents, additives─for enhancing catalytic activity selectivity product discussed in detail. This Review provides detailed insights into recent progress made with a specific focus catalyst development, sources, mechanistic exploration.

Language: Английский

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Production of hydrogen from alcohols via homogeneous catalytic transformations mediated by molecular transition-metal complexes

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(31), P. 4148 - 4169

Published: Jan. 1, 2024

An overview of the state-of-the-art advancements is provided on use transition-metal based molecular catalysts to produce hydrogen from liquid organic carriers (LOHCs) derived renewable sources such as alcohols.

Language: Английский

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Ruthenium Complexes with NNN-Pincer Ligands for N-Methylation of Amines Using Methanol

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(25), P. 11821 - 11831

Published: June 7, 2024

A series of ruthenium complexes (Ru1–Ru4) bearing new NNN-pincer ligands were synthesized in 58–78% yields. All the are air and moisture stable characterized by IR, NMR, high-resolution mass spectra (HRMS). In addition, structures Ru1–Ru3 confirmed X-ray crystallographic analysis. These Ru(II) exhibited high catalytic efficiency broad functional group tolerance N-methylation reaction amines using CH3OH as both C1 source solvent. Experimental results indicated that electronic effect substituents on considerably affects reactivity which Ru3 an electron-donating OMe showed highest activity. Deuterium labeling control experiments suggested dehydrogenation methanol to generate hydride species was rate-determining step reaction. Furthermore, this protocol also provided a ready approach versatile trideuterated N-methylamines under mild conditions CD3OD deuterated methylating agent.

Language: Английский

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Direct use of methanol instead of formaldehyde or paraformaldehyde: Acceptorless dehydrogenative coupling for the synthesis of arylhydrazones catalyzed by a metal–ligand iridium bifunctional catalyst

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 438, P. 115685 - 115685

Published: Aug. 3, 2024

Language: Английский

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SnO_x-Decorated Pt Catalysts for the Reductive N-Methylation of Quinoline with Methanol

ACS Sustainable Chemistry & Engineering, Journal Year: 2024, Volume and Issue: 12(19), P. 7644 - 7654

Published: April 30, 2024

A direct and efficient synthesis of N-methyl-1,2,3,4-tetrahydroquinolines (MTHQs) is achieved through the one-pot reductive N-methylation quinolines. The SnOx-decorated Pt/Al2O3 (Pt-SnOx/Al2O3) catalyst proves to be highly effective in transformation from quinolines MTHQs, using methanol as exclusive source for hydrogen (H) methyl (CH3), without addition additional bases or additives. Mechanistic kinetic studies reveal a tandem reaction pathway: (1) dehydrogenation methanol, (2) reduction 1,2,3,4-tetrahydroquinolines (THQs), (3) THQs with identified rate-determining step. Characterization catalytic performance results demonstrate that SnOx modifies morphology electronic properties Pt-based metal active sites, which dramatically facilitates cleavage O–H less reactive C–H bonds maintains delicate balance between quinolines, thus obtaining high reactivity total transformation.

Language: Английский

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Indoles in Drug Design and Medicinal Chemistry

European Journal of Medicinal Chemistry Reports, Journal Year: 2025, Volume and Issue: unknown, P. 100252 - 100252

Published: Feb. 1, 2025

Language: Английский

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Efficient N-Methylation of Primary Amides Using Methanol Under Mn(I)-Catalysis

Tetrahedron, Journal Year: 2025, Volume and Issue: unknown, P. 134535 - 134535

Published: Feb. 1, 2025

Language: Английский

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Mild oxidative N-formylation of amines with biobased glycolaldehyde over C3N4 supported Cu catalyst under green solvent

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: 508, P. 160963 - 160963

Published: Feb. 27, 2025

Language: Английский

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Artificial Photosynthesis of Formamide via an Oxidant‐Free Photoinduced Radical Coupling Route over Pt‐CdS

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: March 9, 2025

Abstract Large‐scale manufacturing of formamide is always involved with the use carbon monoxide, hence developing a series eco‐friendly synthesis routes great significance. Alternative feedstock low‐cost methanol expected to fulfill this breakthrough due its green and renewable nature; however, overoxidation severely inhibits efficacious from ammonia through conventional catalytic route. Herein, we report successful development direct radical coupling route for converting into high‐selectivity hydrogen without extra oxidants under ambient conditions. The optimized Pt‐CdS photocatalysts offered an impressive production rate 1.45 mmol g −1 h , as well exceptional hole selectivity reaching up 63.5%. oxidant‐free mechanism high‐efficiency generation revealed by in situ characterizations (e.g., electron paramagnetic resonance transient absorption spectroscopy), stems photogenerated holes oxidizing hydroxymethyl subsequently C─N amino radical. This work demonstrates efficient photoinduced strategy promise acceptable alternative current technologies artificial photosynthesis using clean abundant solar energy.

Language: Английский

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Outer-Sphere CO Release Mechanism in the Methanol-to-Syngas Reaction Catalyzed by a Ru-PNP Pincer Complex

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 5113 - 5122

Published: March 12, 2025

Methanol can be used as a surrogate molecule for CO and H2 in the synthesis of large variety chemicals. In this work, mechanism methanol-to-syngas reaction catalyzed by Ru-PNP complex was studied using density functional theory. proposed mechanism, is directly released from methyl formate intermediate, forming Ru-OCH3 species. The preference pathway compared to others literature supported microkinetic model constructed computed Gibbs free energies coupled liquid–vapor batch reactor describing gas phase composition. After including energy corrections ≤6 kcal mol–1 three organic intermediates CO, our could reproduce experimental turnover numbers over time previously reported. Further, evaluate influence solvent polarity methanol concentration on formation products catalyst resting states. These results suggest that methanol, limited thermodynamics, whereas toluene, it Ru–CO formation. Overall, work shows potential models benchmark mechanisms computational methods provide relevant information required design.

Language: Английский

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