Manganese-catalyzed hydrogenation, dehydrogenation, and hydroelementation reactions

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(11), P. 4386 - 4464

Published: Jan. 1, 2022

The emerging field of organometallic catalysis has shifted towards research on Earth-abundant transition metals due to their ready availability, economic advantage, and novel properties. In this case, manganese, the third most abundant transition-metal in Earth's crust, emerged as one leading competitors. Accordingly, a large number molecularly-defined Mn-complexes been synthesized employed for hydrogenation, dehydrogenation, hydroelementation reactions. regard, catalyst design is based three pillars, namely, metal-ligand bifunctionality, ligand hemilability, redox activity. Indeed, developed catalysts not only differ chelating atoms they possess but also working principles, thereby different turnover numbers product molecules. Hence, critical assessment molecularly defined manganese terms atoms, reaction conditions, mechanistic pathway, significant. Herein, we analyze complexes catalytic activity, versatility allow multiple transformations routes convert substrates target This article will be helpful get significant insight into design, aiding design.

Language: Английский

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Recent Advances in Reversible Liquid Organic Hydrogen Carrier Systems: From Hydrogen Carriers to Catalysts

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(37)

Published: Feb. 20, 2024

Abstract Liquid organic hydrogen carriers (LOHCs) have gained significant attention for large‐scale storage due to their remarkable gravimetric capacity (HSC) and compatibility with existing oil gas transportation networks long‐distance transport. However, the practical application of reversible LOHC systems has been constrained by intrinsic thermodynamic properties performances associated catalysts in (de)hydrogenation cycles. To overcome these challenges, thermodynamically favored carriers, high‐performance catalysts, catalytic procedures need be developed. Here, advances recent years summarized, primarily centered on regular catalyzed homogeneous heterogeneous including dehydrogenative aromatization cycloalkanes arenes N ‐heterocyclics ‐heteroarenes, as well reverse hydrogenation processes. Furthermore, development metal complexes coupling, a new family based alcohols is described that can release H 2 under relatively mild conditions. Finally, views next steps challenges field technology are provided, emphasizing resources low‐cost technologies, scenarios.

Language: Английский

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Cobalt-catalyzed dehydrogenative functionalization of alcohols: Progress and future prospect

Coordination Chemistry Reviews, Journal Year: 2021, Volume and Issue: 451, P. 214257 - 214257

Published: Oct. 28, 2021

Language: Английский

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Cooperative approaches in catalytic hydrogenation and dehydrogenation

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(6), P. 1881 - 1898

Published: Jan. 1, 2022

This review uses catalytic hydrogenation and dehydrogenation processes as a platform to compare metal–ligand cooperativity metal–metal strategies in catalysis.

Language: Английский

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Advancement in photocatalytic acceptorless dehydrogenation reactions: Opportunity and challenges for sustainable catalysis

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 472, P. 214805 - 214805

Published: Sept. 3, 2022

Language: Английский

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Well-Defined Phosphine-Free Manganese(II)-Complex-Catalyzed Synthesis of Quinolines, Pyrroles, and Pyridines

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(13), P. 8351 - 8367

Published: June 21, 2022

Herein, we report a simple, phosphine-free, and inexpensive catalytic system based on manganese(II) complex for synthesizing different important N-heterocycles such as quinolines, pyrroles, pyridines from amino alcohols ketones. Several control experiments, kinetic studies, DFT calculations were carried out to support the plausible reaction mechanism. We also detected two potential intermediates in cycle using ESI-MS analysis. Based these metal-ligand cooperative mechanism was proposed.

Language: Английский

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Cobalt-Catalyzed Acceptorless Dehydrogenation of Primary Amines to Nitriles

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(17), P. 11801 - 11810

Published: April 16, 2024

The direct double dehydrogenation from primary amines to nitriles without an oxidant or hydrogen acceptor is both intriguing and challenging. In this paper, we describe a non-noble metal catalyst capable of realizing such transformation with high efficiency. A cobalt-centered N,N-bidentate complex was designed employed as metal–ligand cooperative catalyst. Detailed kinetic studies, control experiments, DFT calculations revealed the crucial hydride transfer, proton evolution processes. Finally, tandem outer-sphere/inner-sphere mechanism proposed for through imine intermediate.

Language: Английский

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Single-Atom Fe-Catalyzed Acceptorless Dehydrogenative Coupling to Quinolines

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(33), P. 23338 - 23347

Published: Aug. 6, 2024

A single-atom iron catalyst was found to exhibit exceptional reactivity in acceptorless dehydrogenative coupling for quinoline synthesis, outperforming known homogeneous and nanocatalyst systems. Detailed characterizations, including aberration-corrected HAADF-STEM, XANES, EXAFS, jointly confirmed the presence of atomically dispersed centers. Various functionalized quinolines were efficiently synthesized from different amino alcohols a range ketones or alcohols. The achieved turnover number (TON) up 10

Language: Английский

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Highly efficient transfer dehydrogenative oxidation of secondary alcohols to ketones catalyzed by NN-manganese complexes

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 430, P. 115337 - 115337

Published: Feb. 1, 2024

Language: Английский

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A Phosphine-Free Air-Stable Mn(II)-Catalyst for Sustainable Synthesis of Quinazolin-4(3H)-ones, Quinolines, and Quinoxalines in Water

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(8), P. 5250 - 5265

Published: March 30, 2024

The synthesis, characterization, and catalytic application of a new phosphine-free, well-defined, water-soluble, air-stable Mn(II)-catalyst [Mn(L)(H2O)2Cl](Cl) ([1]Cl) featuring 1,10-phenanthroline based tridentate pincer ligand, 2-(1H-pyrazol-1-yl)-1,10-phenanthroline (L), in dehydrogenative functionalization alcohols to various N-heterocycles such as quinazolin-4(3H)-ones, quinolines, quinoxalines are reported here. A wide array multisubstituted quinazolin-4(3H)-ones were prepared water under air following two pathways via the coupling with 2-aminobenzamides 2-aminobenzonitriles, respectively. 2-Aminobenzyl alcohol ketones bearing active methylene group used partners for synthesizing quinoline derivatives, quinoxaline derivatives by vicinal diols 1,2-diamines. In all cases, reaction proceeded smoothly using our [1]Cl air, affording desired satisfactory yields starting from cheap readily accessible precursors. Gram-scale synthesis compounds indicates industrial relevance synthetic strategy. Control experiments performed understand unveil plausible mechanism.

Language: Английский

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