The Origin of Shape Sensitivity in Palladium‐Catalyzed Suzuki–Miyaura Cross Coupling Reactions

Collins, Gillian; Schmidt, Michael; O’Dwyer, Colm; Holmes, Justin D.; McGlacken, Gerard P.

doi:10.1002/anie.201400483

Cited by 129 publications

(110 citation statements)

References 57 publications

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“…Noble metal nanoparticles (NPs) and their alloys are of interest to wide range of areas such as electronics 1 , photovoltaics 2 , biomedical and catalysis 3 . Silver (Ag) and gold (Au) NPs are particularly important due to their unique optical properties which enables a range of applications such as surface enhanced Raman scattering (SERS) 4 , plasmonic sensors 5 , bioimaging and cancer therapy.…”

Section: Introductionmentioning

confidence: 99%

Controlling alloy formation and optical properties by galvanic replacement of sub-20 nm silver nanoparticles in organic media

2015

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Section: Introductionmentioning

confidence: 99%

Controlling alloy formation and optical properties by galvanic replacement of sub-20 nm silver nanoparticles in organic media

2015

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“…[12] The structure dependent activity trend was found to be cubic > cuboctahedra > octahedral NPs. A combination of TEM, inductively coupled plasma (ICP) and x-ray photoelectron spectroscopy (XPS), revealed that the reactivity trend originated from the facetpreferred dissolution of the (100)-enclosed cubic NPs.…”

Section: Designing Catalytic Nanoparticles To Probe Reaction Mechanismsmentioning

confidence: 94%

Engineering Metallic Nanoparticles for Enhancing and Probing Catalytic Reactions

Collins

Holmes

2016

Advanced Materials

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Type of publicationArticle (peer-reviewed) AbstractRecent developments in tailoring the structural and chemical properties of colloidal nanoparticles (NPs) have led to significant enhancements in catalyst performance. Controllable colloidal NP synthesis has also allowed tailor-made NPs to also serve as mechanistic probes for catalytic processes. The innovative use of colloidal NPs to gain fundamental insights into catalytic function will be highlighted across a variety of catalytic applications. The future engineering of catalyst NPs is also moving beyond size, shape and composition considerations.Advancements in understanding structure-property relationships have enabled incorporation of complex features such as tuning surface strain to influence the behaviour of catalytic NPs.Exploiting plasmonic properties of NPs and altering colloidal surface chemistry through functionalization are also emerging as important areas for rational design of catalytic NPs. This news article will highlight the key developments and challenges to future design of catalytic NPs.

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“…According to Gaikwad et al [56] Pd 0 atom and Pd II ion leach simultaneously and this simultaneous leaching underpins the catalysis in the SMXR. High-index surface facets have also been correlated with high catalytic activity as a result of increased Pd leaching [57,58].…”

Section: The Mechanism Of Catalysis By Nanoparticles-on the Surface Omentioning

confidence: 99%

Halide-Enhanced Catalytic Activity of Palladium Nanoparticles Comes at the Expense of Catalyst Recovery

et al. 2017

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Abstract:In this communication, we present studies of the oxidative homocoupling of arylboronic acids catalyzed by immobilised palladium nanoparticles in aqueous solution. This reaction is of significant interest because it shares a key transmetallation step with the well-known Suzuki-Miyaura cross-coupling reaction. Additives can have significant effects on catalysis, both in terms of reaction mechanism and recovery of catalytic species, and our aim was to study the effect of added halides on catalytic efficiency and catalyst recovery. Using kinetic studies, we have shown that added halides (added as NaCl and NaBr) can increase the catalytic activity of the palladium nanoparticles more than 10-fold, allowing reactions to be completed in less than half a day at 30 • C. However, this increased activity comes at the expense of catalyst recovery. The results are in agreement with a reaction mechanism in which, under conditions involving high concentrations of chloride or bromide, palladium leaching plays an important role. Considering the evidence for analogous reactions occurring on the surface of palladium nanoparticles under different reaction conditions, we conclude that additives can exert a significant effect on the mechanism of reactions catalyzed by nanoparticles, including switching from a surface reaction to a solution reaction. The possibility of this switch in mechanism may also be the cause for the disagreement on this topic in the literature.

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The Origin of Shape Sensitivity in Palladium‐Catalyzed Suzuki–Miyaura Cross Coupling Reactions

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Cited by 129 publications

References 57 publications

Controlling alloy formation and optical properties by galvanic replacement of sub-20 nm silver nanoparticles in organic media

Controlling alloy formation and optical properties by galvanic replacement of sub-20 nm silver nanoparticles in organic media

Engineering Metallic Nanoparticles for Enhancing and Probing Catalytic Reactions

Halide-Enhanced Catalytic Activity of Palladium Nanoparticles Comes at the Expense of Catalyst Recovery

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