Reversible hydrogenation of carbon dioxide to formic acid using a Mn-pincer complex in the presence of lysine

Nature Energy, Journal Year: 2022, Volume and Issue: 7(5), P. 438 - 447

Published: May 19, 2022

Abstract Efficient hydrogen storage and release are essential for effective use of as an energy carrier. In principle, formic acid could be used a convenient medium via reversible CO 2 hydrogenation. However, noble metal-based catalysts currently needed to facilitate the (de)hydrogenation, produced during is generally released, resulting in undesirable emissions. Here we report α -amino acid-promoted system hydrogenation using Mn-pincer complex homogeneous catalyst. We observe good stability reusability catalyst lysine amino at high productivities (CO hydrogenation: total turnover number 2,000,000; dehydrogenation: 600,000). Employing potassium lysinate, achieve >80% H evolution efficiency >99.9% retention ten charge–discharge cycles, avoiding re-loading steps between each cycle. This process was scaled up by factor 18 without obvious drop productivity.

Language: Английский

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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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Towards ligand simplification in manganese-catalyzed hydrogenation and hydrosilylation processes

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 458, P. 214421 - 214421

Published: Jan. 31, 2022

Language: Английский

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Manganese(I)-catalyzed asymmetric (transfer) hydrogenation of ketones: An insight into the effect of chiral PNN and NN ligands

Journal of Catalysis, Journal Year: 2023, Volume and Issue: 418, P. 40 - 50

Published: Jan. 7, 2023

Language: Английский

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Organometallic Mn(I) Complexes in Asymmetric Catalytic (Transfer) Hydrogenation and Related Transformations

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(14)

Published: March 7, 2024

Abstract Direct asymmetric hydrogenation (AH) and transfer (ATH) are among the most efficient approaches to produce chiral building blocks. Recently, these types of transformations have witnessed a shift towards use molecular catalysts based on earth‐abundant transition metals due their ready availability, economic advantage, novel properties. With particular regard manganese, catalyst development has seen both efficiency substrate scope in AH ATH greatly improved, with emergence large number well‐defined Mn‐complexes employed this field. The reaction includes C=O bonds, reduction C=N bonds reductive C=C bonds. Herein, our survey area focuses catalytic activity such complexes, versatility routes convert substrates target molecules. We consider collected findings article will be helpful reader by providing an insight into ligand design, thereby aiding future development. Moreover, review is aimed at highlighting remarkable progress made last seven years manganese complexes for enantioselective reduction.

Language: Английский

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Cycloheptyl-fused-PNN-manganese catalyzed asymmetric transfer hydrogenation of ketones

Molecular Catalysis, Journal Year: 2024, Volume and Issue: 564, P. 114274 - 114274

Published: June 8, 2024

Language: Английский

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Manganese‐Catalyzed Asymmetric Formal Hydroamination of Allylic Alcohols: A Remarkable Macrocyclic Ligand Effect

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(26)

Published: April 19, 2022

A unique family of chiral peraza N6 -macrocyclic ligands, which are conformationally rigid and have a tunable saddle-shaped cavity, is described. Utilizing their manganese(I) complexes, the first example earth-abundant transition metal-catalyzed asymmetric formal anti-Markovnikov hydroamination allylic alcohols was realized, providing practical access to synthetically important γ-amino in excellent yields enantioselectivities (up 99 % yield 98 ee). The single-crystal structure MnI complex indicates that manganese atom coordinates with dialkylamine moiety bidentate fashion. Further DFT calculations revealed five six nitrogen atoms ligand were engaged multiple noncovalent interactions Mn, an isopropanol molecule, β-amino ketone intermediate via coordination, hydrogen bonding, and/or CH⋅⋅⋅π state, showing remarkable role macrocyclic framework.

Language: Английский

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Stereoselective Semi‐Hydrogenations of Alkynes by First‐Row (3d) Transition Metal Catalysts

ChemCatChem, Journal Year: 2022, Volume and Issue: 14(20)

Published: Aug. 26, 2022

The chemo- and stereoselective semi-hydrogenation of alkynes to alkenes is a fundamental transformation in synthetic chemistry, for which the use precious 4d or 5d metal catalysts well-established. In mankind's unwavering quest sustainability, research focus has considerably veered towards 3d metals. Given their high abundancy availability as well lower toxicity noxiousness, they are undoubtedly attractive from both an economic environmental perspective. Herein, we wish present noteworthy groundbreaking examples diastereoselective alkyne embark on journey through first-row transition

Language: Английский

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Performance of homogeneous catalysts viewed in dynamics

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(13), P. 1757 - 1768

Published: Jan. 1, 2023

In this feature article, we discuss how the different aspects of complex catalytic mechanisms manifest themselves in commonly accepted performance metrics.

Language: Английский

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Recent Developments in Manganese, Iron and Cobalt Homogeneous Catalyzed Synthesis of Primary Amines via Reduction of Nitroarenes, Nitriles and Carboxamides

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(7), P. 948 - 964

Published: Feb. 18, 2023

Abstract The preparation of primary amines attracts huge attention in the molecular synthetic community. Indeed, play a crucial role chemistry as they are important substructures amount drug molecules, agrochemicals, dyes and materials. Compared to stoichiometric reductions using metal hydride based reagents, catalyzed reduction nitroarenes, nitriles carboxamides appears be an attractive option, mainly when associated first row transition metals such manganese, iron, or cobalt. In this short review, we illustrate progress achieved homogeneous hydrogenation, hydrogen transfer, borrowing hydrosilylation carboxamides. magnified image

Language: Английский

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