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

Nature Energy, Год журнала: 2022, Номер 7(5), С. 438 - 447

Опубликована: Май 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.

Язык: Английский

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Manganese-catalyzed hydrogenation, dehydrogenation, and hydroelementation reactions

Chemical Society Reviews, Год журнала: 2022, Номер 51(11), С. 4386 - 4464

Опубликована: Янв. 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.

Язык: Английский

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Towards ligand simplification in manganese-catalyzed hydrogenation and hydrosilylation processes

Coordination Chemistry Reviews, Год журнала: 2022, Номер 458, С. 214421 - 214421

Опубликована: Янв. 31, 2022

Язык: 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, Год журнала: 2023, Номер 418, С. 40 - 50

Опубликована: Янв. 7, 2023

Язык: Английский

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

ChemCatChem, Год журнала: 2024, Номер 16(14)

Опубликована: Март 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.

Язык: Английский

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

Molecular Catalysis, Год журнала: 2024, Номер 564, С. 114274 - 114274

Опубликована: Июнь 8, 2024

Язык: Английский

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The importance of alkali cations in manganese-catalyzed enantioselective transfer hydrogenation of ketones: An insight into the effect of “NH” and “C N” groups in ligands

Journal of Catalysis, Год журнала: 2025, Номер unknown, С. 115998 - 115998

Опубликована: Фев. 1, 2025

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(26)

Опубликована: Апрель 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.

Язык: Английский

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

ChemCatChem, Год журнала: 2022, Номер 14(20)

Опубликована: Авг. 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

Язык: Английский

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Homogeneous Manganese-Catalyzed Hydrofunctionalizations of Alkenes and Alkynes: Catalytic and Mechanistic Tendencies

ACS Omega, Год журнала: 2022, Номер 7(42), С. 37008 - 37038

Опубликована: Окт. 11, 2022

In recent years, many manganese-based homogeneous catalytic precursors have been developed as powerful alternatives in organic synthesis. Among these, the hydrofunctionalizations of unsaturated C–C bonds correspond to outstanding ways afford compounds with more versatile functional groups, which are commonly used building blocks production fine chemicals and feedstock for industrial field. Herein, we present an account Mn-catalyzed alkenes alkynes main objective finding mechanistic tendencies that could serve a platform works come.

Язык: Английский

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