Toward Active-Site Tailoring in Heterogeneous Catalysis by Atomically Precise Metal Nanoclusters with Crystallographic Structures

Chemical Reviews, Journal Year: 2020, Volume and Issue: 121(2), P. 567 - 648

Published: Sept. 17, 2020

Heterogeneous catalysis involves solid-state catalysts, among which metal nanoparticles occupy an important position. Unfortunately, no two from conventional synthesis are the same at atomic level, though such regular can be highly uniform nanometer level (e.g., size distribution ∼5%). In long pursuit of well-defined nanocatalysts, a recent success is atomically precise nanoclusters protected by ligands in range tens to hundreds atoms (equivalently 1–3 nm core diameter). More importantly, have been crystallographically characterized, just like protein structures enzyme catalysis. Such merge features homogeneous catalysts ligand-protected centers) and enzymes protein-encapsulated clusters few bridged ligands). The with their total available constitute new class model hold great promise fundamental research, including dependent activity, control catalytic selectivity structure surface ligands, structure–property relationships atomic-level, insights into molecular activation mechanisms, identification active sites on nanocatalysts. This Review summarizes progress utilization for These nanocluster-based enabled heterogeneous research single-atom single-electron levels. Future efforts expected achieve more exciting understanding tailoring design high activity under mild conditions.

Language: Английский

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Homogeneous manganese-catalyzed hydrogenation and dehydrogenation reactions

Chem, Journal Year: 2020, Volume and Issue: 7(5), P. 1180 - 1223

Published: Dec. 9, 2020

Language: Английский

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Strain Engineering in Electrocatalysts: Fundamentals, Progress, and Perspectives

Advanced Energy Materials, Journal Year: 2021, Volume and Issue: 12(5)

Published: Dec. 22, 2021

Abstract Strain engineering of nanomaterials, namely, designing, tuning, or controlling surface strains nanomaterials is an effective strategy to achieve outstanding performance in different for their various applications. This article summarizes recent progress and achievements the development strain‐rich electrocatalysts (SREs) applications field electrochemical energy conversion technologies. It starts from definition lattice strains, followed by classification where mechanisms strain formation reported methods regulate related are elaborated. The SRE characterization techniques overviewed, focusing deeply on clarification strain‐property relationship these SREs. Their electrocatalytic reactions further highlighted, including hydrogen evolution reaction, oxygen reduction alcohol oxidation carbon dioxide nitrogen reaction. Related reaction SREs interpreted after taking catalytic performance, as well between properties into account. challenges future opportunities finally outlined discussed together with potential fields.

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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Construction of Monophosphine–Metal Complexes in Privileged Diphosphine-Based Covalent Organic Frameworks for Catalytic Asymmetric Hydrogenation

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(11), P. 6100 - 6111

Published: March 10, 2023

Privileged diphosphine ligands that chelate many transition metals to form stable chelation complexes are essential in a variety of catalytic processes. However, the exact identity catalytically active moieties remains ambiguous because chelated metal catalysts may undergo rearrangement during catalysis produce monophosphine-metal complexes, which hard isolate and evaluate activities. By taking advantage isolation two phosphorus atoms, we demonstrate here successful construction chiral monophosphine-Ir/Ru covalent organic frameworks (COFs) for enantioselective hydrogenation. condensation tetraaldehyde enantiopure MeO-BIPHEP linear aromatic diamines, prepare homochiral two-dimensional COFs with ABC stacking, P atoms each separated fixed far apart. Post-synthetic metalations thus afford single-site Ir/Ru-monophosphine catalysts, contrast homogeneous analogues, demonstrated excellent recyclable performance asymmetric hydrogenation quinolines β-ketoesters, affording up 99.9% enantiomeric excess. Owing fact porous catalyst is capable adsorbing concentrating hydrogen, reactions promoted under ambient/medium pressure, typically performed high pressure catalysis. This work not only shows diphosphines can be centers but also provides new strategy types privileged phosphine-based heterogeneous catalysts.

Language: Английский

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Manganese‐Catalyzed Asymmetric Hydrogenation of Quinolines Enabled by π–π Interaction**

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(10), P. 5108 - 5113

Published: Nov. 26, 2020

Abstract The non‐noble metal‐catalyzed asymmetric hydrogenation of N‐heteroaromatics, quinolines, is reported. A new chiral pincer manganese catalyst showed outstanding catalytic activity in the affording high yields and enantioselectivities (up to 97 % ee). turnover number 3840 was reached at a low loading (S/C=4000), which competitive with most effective noble metal catalysts for this reaction. precise regulation enantioselectivity were ensured by π–π interaction.

Language: Английский

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Cobalt-catalyzed highly enantioselective hydrogenation of α,β-unsaturated carboxylic acids

Nature Communications, Journal Year: 2020, Volume and Issue: 11(1)

Published: June 26, 2020

Asymmetric hydrogenation of α,β-unsaturated acids catalyzed by noble metals has been well established, whereas, the asymmetric with earth-abundant-metal was rarely reported. Here, we describe a cobalt-catalyzed carboxylic acids. By using chiral cobalt catalyst bearing electron-donating diphosphine ligand, high activity (up to 1860 TON) and excellent enantioselectivity >99% ee) are observed. Furthermore, is successfully applied broad spectrum acids, such as various α-aryl α-alkyl cinnamic acid derivatives, α-oxy-functionalized α-substituted acrylic heterocyclic (30 examples). The synthetic utility protocol highlighted synthesis key intermediates for drugs (6 cases). Preliminary mechanistic studies reveal that carboxy group may be involved in control reactivity through an interaction metal centre.

Language: Английский

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Enantioselective Hydrogenation of Tetrasubstituted α,β‐Unsaturated Carboxylic Acids Enabled by Cobalt(II) Catalysis: Scope and Mechanistic Insights

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(20), P. 11384 - 11390

Published: Feb. 19, 2021

Abstract Chiral carboxylic acids are important compounds because of their prevalence in pharmaceuticals, natural products and agrochemicals. Asymmetric hydrogenation α,β‐unsaturated has been widely recognized as one the most efficient synthetic approaches to afford such compounds. Although related asymmetric di‐ trisubstituted unsaturated with noble metals is well established, challenging tetrasubstituted rarely reported. We demonstrate enantioselective cyclic acyclic via cobalt(II) catalysis. This protocol showed broad substrate scope gave chiral good yields excellent enantiocontrol (up 98 % yield 99 ee ). Combined experimental computational mechanistic studies support a Co II catalytic cycle involving migratory insertion σ‐bond metathesis processes. DFT calculations reveal that enantioselectivity may originate from steric effect between phenyl groups ligand substrate.

Language: Английский

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Manganese(I)-Catalyzed H–P Bond Activation via Metal–Ligand Cooperation

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(48), P. 20071 - 20076

Published: Nov. 19, 2021

Here we report that chiral Mn(I) complexes are capable of H-P bond activation. This activation mode enables a general method for the hydrophosphination internal and terminal α,β-unsaturated nitriles. Metal-ligand cooperation, strategy previously not considered catalytic activation, is at base mechanistic action Mn(I)-based catalyst. Our computational studies support stepwise mechanism provide insight into origin enantioselectivity.

Language: Английский

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Structure, reactivity and catalytic properties of manganese-hydride amidate complexes

Nature Chemistry, Journal Year: 2022, Volume and Issue: 14(11), P. 1233 - 1241

Published: Sept. 12, 2022

Language: Английский

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