A comparative study on atomically precise Au nanoclusters as catalysts for the aldehyde–alkyne–amine (A<sup>3</sup>) coupling reaction: ligand effects on the nature of the catalysis and efficiency

Li, Yingzhou; Leong, Weng Kee

doi:10.1039/c9ra00933g

Cited by 10 publications

(12 citation statements)

References 28 publications

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“…reported a shortening of the A 3 -coupling reaction time from hours to minutes at higher temperatures (175 °C) using a more thermally robust, trimetallic Au 1 Ag 16 Cu 12 (SSR) 12 (PPh 3 ) 4 nanocluster (where SSR = benzene-1,3-dithiolate), indicating the potential of alloying in catalytic enhancement . In addition, Li and Leong reported the stibine-protected Au 13 for the A 3 -coupling reaction with a higher activity than the NCs stabilized by thiolate and phosphine ligands, in which the weaker coordination of stibine was invoked to explain this observation …”

Section: Paradigms Of Nanocluster-based Catalysismentioning

confidence: 99%

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

et al. 2020

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

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Section: Paradigms Of Nanocluster-based Catalysismentioning

confidence: 99%

“…198 In addition, Li and Leong reported the stibine-protected Au 13 for the A 3 -coupling reaction with a higher activity than the NCs stabilized by thiolate and phosphine ligands, in which the weaker coordination of stibine was invoked to explain this observation. 199 3.1.5. Electrochemical CO 2 Reduction Reaction.…”

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confidence: 99%

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

et al. 2020

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“…To probe our hypothesis that the catalytically active site is the central gold atom in the PAu−Au−AuP structural motifs, we also examined the reactivity of known full‐phosphine‐protected gold and gold–silver clusters [Au 6 C], [Au 6 Ag 4 C], nanogold clusters nano‐[Au 6 ] and [Au 13 ] . However, none of these species displayed catalytic activity in the addition of 1,3,5‐trimethoxybenzene to 1,6‐enyne 10 at 25 °C…”

Section: Resultsmentioning

confidence: 99%

Small Gold(I) and Gold(I)–Silver(I) Clusters by C−Si Auration

Pei

Pereira

Smirnova

et al. 2020

Chemistry A European J

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Auration of o‐trimethylsilyl arylphosphines leads to the formation of gold and gold–silver clusters with ortho‐metalated phosphines displaying 3c–2e Au−C−M bonds (M=Au/Ag). Hexagold clusters [Au6L4](X)2 are obtained by reaction of (L−TMS)AuCl with AgX, whereas reaction with AgX and Ag2O leads to gold–silver clusters [Au4Ag2L4](X)2. Oxo‐trigold(I) species [Au3O]+ were identified as the intermediates in the formation of the silver‐doped clusters. Other [Au5], [Au4Ag], and [Au12Ag4] clusters were also obtained. Clusters containing PAu−Au−AuP structural motif display good catalytic activity in the activation of alkynes under homogeneous conditions.

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“…[ 6‐11 ] Increase of unsaturated sites on the surface (surface effect) enables the clusters to exhibit good catalytic activity and unique selectivity in reactions such as oxidation ( Au 38 , Au 144 ), hydrogenation ( Cu 25 ), C—C coupling ( Au 11 , Cu 53 ), A 3 coupling ( Au 13 ), cycloaddition ( Cu 20 ), etc . [ 12‐17 ] Nanoclusters with precise structures can also serve as model catalysts to reveal the correlation between catalyst performance and structure. [ 18 ] The well‐defined compositions and atomically precise molecular structures of MPCs are the basis for elucidating their structure‐ composition‐property relationships and size evolution mechanisms.…”

Section: Background and Originality Contentmentioning

confidence: 99%

Kernels‐Different Au₂₅Nanoclusters Enhanced Catalytic Performance via Modification of Ligand and Electronic Effects

Xue

Wei

et al. 2022

Chin. J. Chem.

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Ultrasmall atomically precise thiolate-protected gold nanoclusters with surface open sites are crucial for practical applications in catalysis. However, there is a lack of systematic studies that unify the kernels-isomerization, modification of peripheral ligands and electronic effects into one system, as well as their correlation to catalytic performances. In this work, three structurally related Au 25 nanoclusters with reported star Au 25 kernels, Au 25 -i-FTP, Au 25 -bi-FTP, and Au 25 -bi-CHT have been synthesized through two different methods: one-pot direct reduction and two-step reduction by using AsPh 3 as converter. Their structures and catalytic performance have been comparatively investigated. Au 25 -i-FTP has a classic Au 13 core capped by six dimeric RS-Au-SR-Au-SRs, while Au 25 -bi-FTP and Au 25 -bi-CHT feature typical rod-shaped biicosahedral geometric kernel. All of the three Au 25 clusters were effective catalysts for oxidation of organosilanes, different from conclusions obtained in literature. Especially, the nanorod-type Au 25 -bi-CHT clusters protected by flexible thiol ligands showed very good catalytic performance in this reaction, the conversion and selectivity were close to 100% within 5 min. The ligand rigidity and electron effects work together to modulate the catalytic properties. The findings inspire us to rethink kernel and ligand effects on catalytic property, and the principle demonstrated here will possibly be widely-used in high active atom-precise catalysts modification.

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A comparative study on atomically precise Au nanoclusters as catalysts for the aldehyde–alkyne–amine (A³) coupling reaction: ligand effects on the nature of the catalysis and efficiency

Abstract: A stibine-stabilised gold nanocluster which acts as a homogeneous catalyst in the A3 coupling reaction.

Cited by 10 publications

References 28 publications

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

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

Small Gold(I) and Gold(I)–Silver(I) Clusters by C−Si Auration

Kernels‐Different Au₂₅Nanoclusters Enhanced Catalytic Performance via Modification of Ligand and Electronic Effects

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A comparative study on atomically precise Au nanoclusters as catalysts for the aldehyde–alkyne–amine (A3) coupling reaction: ligand effects on the nature of the catalysis and efficiency

Abstract: A stibine-stabilised gold nanocluster which acts as a homogeneous catalyst in the A3 coupling reaction.

Cited by 10 publications

References 28 publications

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

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

Small Gold(I) and Gold(I)–Silver(I) Clusters by C−Si Auration

Kernels‐Different Au25Nanoclusters Enhanced Catalytic Performance via Modification of Ligand and Electronic Effects

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A comparative study on atomically precise Au nanoclusters as catalysts for the aldehyde–alkyne–amine (A³) coupling reaction: ligand effects on the nature of the catalysis and efficiency

Kernels‐Different Au₂₅Nanoclusters Enhanced Catalytic Performance via Modification of Ligand and Electronic Effects