Transition metal ‘cocktail’-type catalysis

Prima, Darya O.; Kulikovskaya, Natalia S.; Galushko, Alexey S.; Mironenko, Roman M.; Ananikov, Valentine P.

doi:10.1016/j.cogsc.2021.100502

Cited by 42 publications

(56 citation statements)

References 55 publications

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“…When the Pd‐NHC bond is broken, soluble metal complexes are transformed to Pd clusters and nanoparticles, and a “cocktail”‐type catalytic system is formed (metal complexes and nanoparticles may simultaneously be present in the reaction mixture). [ 24 ]…”

Section: Resultsmentioning

confidence: 99%

“…When the Pd-NHC bond is broken, soluble metal complexes are transformed to Pd clusters and nanoparticles, and a "cocktail"-type catalytic system is formed (metal complexes and nanoparticles may simultaneously be present in the reaction mixture). [24] To independently confirm eNMR spectral evidence about catalyst transformation from molecular to nanoscale type, the formation of the nanoparticles was determined experimentally using SEM/TEM electron microscopy (Supporting Information, pages S9-S10). Thus, the overall character of the studied process was confirmed (Figure 1).…”

Section: Study Of a Catalytic Reactionmentioning

confidence: 99%

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A novel approach to study catalytic reactions via electrophoretic NMR on the example of Pd/NHC‐catalyzed Mizoroki–Heck cross‐coupling reaction

Kulikovskaya

Denisova

Ananikov

2022

Magnetic Reson in Chemistry

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Investigation of catalytic reactions using nuclear magnetic resonance (NMR) is a crucial task, which is often challenging to perform due to rather complex transformations at the metal center. In this work, it was shown that electrophoretic NMR can be a suitable method for studying catalytic reactions and for observing the changes in the catalyst nature. As an important example involving palladium catalysts with N‐heterocyclic carbine ligands (NHCs), the breakage of the Pd‐NHC bond can occur during the catalytic process. Electrophoretic NMR allows the distinction of compounds in the spectra depending on the charge, thus bringing new opportunities to mechanistic studies. Here, we present independent evidence of R‐NHC product formation in the Pd‐catalyzed Mizoroki–Heck reaction—the key process for catalyst change from the molecular to nano‐scale type.

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Section: Resultsmentioning

confidence: 99%

Section: Study Of a Catalytic Reactionmentioning

confidence: 99%

A novel approach to study catalytic reactions via electrophoretic NMR on the example of Pd/NHC‐catalyzed Mizoroki–Heck cross‐coupling reaction

Kulikovskaya

Denisova

Ananikov

2022

Magnetic Reson in Chemistry

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“…5 In a series of papers published since the early 2010s, Ananikov's and Beletskaya's teams reported the discovery that most catalytic reactions mediated by noble metal nanoparticles, metal salts and metal complexes in liquid phase actually involve a "cocktail"-type of catalysis in which solid nanoparticles, metal clusters in solution, and soluble metal complexes formed upon leaching all take part in catalytic cycles. 6,7 In the case of a organosilica-entrapped palladium complex sol-gel catalyst, indeed, both homogeneous and heterogeneous catalysis are involved. 8 In cross-coupling reactions, for example, substrates such as iodo-aryls react with the surface of the catalyst to generate hyperactive soluble Pd(II) complexes that, even though present in trace amounts, are responsible for the catalysis observed.…”

Section: Introductionmentioning

confidence: 99%

Shape and stability matter: enhanced catalytic reactions via sol-gel entrapped catalysts

Ciriminna

Pagliaro

2022

Preprint

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The morphology and the unique chemical and physical stability of organosilica-entrapped sol-gel catalysts allow to apply them to successfully mediate the synthesis of a wide variety of valued molecules, including polymers, manufactured by the fine chemical industry. Referring to selected independent research achievements, in this study we offer a practically oriented insight on these catalytic materials that will hopefully be useful in renewed, unified catalysis education aimed to foster practically relevant innovation and uptake of heterogeneous catalysis in the fine chemical industry.

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“…The concept of a catalyst cocktail is an important model for describing the transformations of catalyst particles in solution [1][2][3]. This model suggests the participation of various types of catalytically active particles that can form when using supported metal catalysts, in the catalytic cycle.…”

Section: Introductionmentioning

confidence: 99%

How to Make a Cocktail of Palladium Catalysts with Cola and Alcohol: Heteroatom Doping vs. Nanoscale Morphology of Carbon Supports

et al. 2021

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Sparkling drinks such as cola can be considered an affordable and inexpensive starting material consisting of carbohydrates and sulfur- and nitrogen-containing organic substances in phosphoric acid, which makes them an excellent precursor for the production of heteroatom-doped carbon materials. In this study, heteroatom-doped carbon materials were successfully prepared in a quick and simple manner using direct carbonization of regular cola and diet cola. The low content of carbon in diet cola allowed reaching a higher level of phosphorus in the prepared carbon material, as well as obtaining additional doping with nitrogen and sulfur due to the presence of sweeteners and caffeine. Effects of carbon support doping with phosphorus, nitrogen and sulfur, as well as of changes in textural properties by ball milling, on the catalytic activity of palladium catalysts were investigated in the Suzuki–Miyaura and Mizoroki–Heck reactions. Contributions of the heteroatom doping and specific surface area of the carbon supports to the increased activity of supported catalysts were discussed. Additionally, the possibility of these reactions to proceed in 40% potable ethanol was studied. Moreover, transformation of various palladium particles (complexes and nanoparticles) in the reaction medium was detected by mass spectrometry and transmission electron microscopy, which evidenced the formation of a cocktail of catalysts in a commercial 40% ethanol/water solution.

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Transition metal ‘cocktail’-type catalysis

Cited by 42 publications

References 55 publications

A novel approach to study catalytic reactions via electrophoretic NMR on the example of Pd/NHC‐catalyzed Mizoroki–Heck cross‐coupling reaction

A novel approach to study catalytic reactions via electrophoretic NMR on the example of Pd/NHC‐catalyzed Mizoroki–Heck cross‐coupling reaction

Shape and stability matter: enhanced catalytic reactions via sol-gel entrapped catalysts

How to Make a Cocktail of Palladium Catalysts with Cola and Alcohol: Heteroatom Doping vs. Nanoscale Morphology of Carbon Supports

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