New Endeavors in Gold Catalysis—Size Matters

Gramage‐Doria, Rafael; Reek, Joost N. H.

doi:10.1002/anie.201307205

Cited by 10 publications

(8 citation statements)

References 40 publications

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“…In gold catalysis, many efforts have been devoted in the rational design of ligands based on large backbones. 357 It was envisioned that size effects could influence both the metal center and the activated substrates and consequently, the outcome of the process. 19 To achieve this aim, there are a few strategies to follow such as (i) the use of reversible interactions to prepare the ligand scaffold, (ii) based on multiple catalyst- substrate interactions, (iii) encapsulation of the gold-based catalyst, and (iv) using supramolecular regulation of the activity of the catalytic system.…”

Section: Sterically Hindered Gold Complexesmentioning

confidence: 99%

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Main Avenues in Gold Coordination Chemistry

2021

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In this contribution, we provide an overview of the main avenues that have emerged in gold coordination chemistry during the last years. The unique properties of gold have motivated research in gold chemistry, and especially regarding the properties and applications of gold compounds in catalysis, medicine, and materials chemistry. The advances in the synthesis and knowledge of gold coordination compounds have been possible with the design of novel ligands becoming relevant motifs that have allowed the preparation of elusive complexes in this area of research. Strong donor ligands with easily modulable electronic and steric properties, such as stable singlet carbenes or cyclometalated ligands, have been decisive in the stabilization of gold(0) species, gold fluoride complexes, gold hydrides, unprecedented π complexes, or cluster derivatives. These new ligands have been important not only from the fundamental structure and bonding studies but also for the synthesis of sophisticated catalysts to improve activity and selectivity of organic transformations. Moreover, they have enabled the facile oxidative addition from gold(I) to gold(III) and the design of a plethora of complexes with specific properties.

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Section: Sterically Hindered Gold Complexesmentioning

confidence: 99%

“…In gold catalysis, many efforts have been devoted in the rational design of ligands based on large backbones . It was envisioned that size effects could influence both the metal center and the activated substrates and consequently, the outcome of the process .…”

Section: Sophisticated Gold Catalystsmentioning

confidence: 99%

Main Avenues in Gold Coordination Chemistry

2021

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“…2 The properties of nanoparticles strongly depend on their size, shape, crystallinity and structure, which determine their specic applications. 3 In particular, metal nanoparticles with high-index facet surfaces exhibit fascinating surface-enhanced and catalytic properties compared to spherical ones. 4 It was recently shown that Au nanoparticles with high-index facets exhibit facet-dependent catalytic activities.…”

Section: Introductionmentioning

confidence: 99%

Temperature-induced Au nanostructure synthesis in a nonaqueous deep-eutectic solvent for high performance electrocatalysis

et al. 2015

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Structure-controlled synthesis of gold nanostructures (AuNSs) induced by temperature in a nonaqueous urea-choline chloride deep eutectic solvent (DES) is reported. Modulation of nanostructures with welldefined structures and shapes is obtained by simply varying the reaction temperature. The supramolecular soft template provided by the DES structure and its viscosity at different temperatures drives directed growth of crystalline gold and self-assembly producing star-shaped AuNSs. Additionally, the effect of AuNS shape and surface area on their catalytic activity towards the reduction of hydrogen peroxide (H 2 O 2 ) has been tested. With the advantage of their high surface area and presence of highindex facets in the edge of the star arms, the star-shaped nanostructures showed superior electrocatalytic activity than other morphologies. The use of DES as a green chemistry platform for the synthesis of shape-controlled Au nanostructures with high catalytic properties may offer new avenues for fuel cell and biosensor applications.

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“…On the other hand, tunability and mechanistic understanding for heterogeneous catalysts are more difficult compared to homogeneous catalysts due to their structural complexity. In recent years, heterogeneous catalysts are being “downsized” to the point that they are becoming “molecular” in order to achieve higher activity and/or better atom economy, − while homogeneous catalysts are being “heterogenized” on surfaces. For the latter, anchoring strategies are necessary, including electropolymerization and anchoring groups such as carboxylates and phosphonates. − Synthetic procedures to introduce and to deprotect these groups are often challenging and are required to be tolerated by the molecules where they are being introduced.…”

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confidence: 99%

Self-Assembled Bilayers as an Anchoring Strategy: Catalysts, Chromophores, and Chromophore-Catalyst Assemblies

2019

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Anchoring strategies for immobilization of molecular catalysts, chromophores, and chromophore-catalyst assemblies on electrode surfaces play an important role in solar energy conversion devices such as dye-sensitized solar cells and dye-sensitized photoelectrosynthesis cells. They are also important in interfacial studies with surface-bound molecules including electron-transfer dynamics and mechanistic studies related to small molecule activation catalysis. Significant progress has been made in this area, but many challenges remain in terms of stability, synthetic complexity, and versatility. We report here a new anchoring strategy based on self-assembled bilayers. This strategy takes advantage of noncovalent interactions between long alkyl chains chemically bound to a metal-oxide electrode surface and long alkyl chains on the molecule being anchored. The new methodology is applicable to the heterogenization of both catalysts and chromophores as well as to the in situ “synthesis” of chromophore-catalyst assemblies on the electrode surface.

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New Endeavors in Gold Catalysis—Size Matters

Cited by 10 publications

References 40 publications

Main Avenues in Gold Coordination Chemistry

Main Avenues in Gold Coordination Chemistry

Temperature-induced Au nanostructure synthesis in a nonaqueous deep-eutectic solvent for high performance electrocatalysis

Self-Assembled Bilayers as an Anchoring Strategy: Catalysts, Chromophores, and Chromophore-Catalyst Assemblies

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