Examination of Pt<sub>2</sub>dba<sub>3</sub> as a “cocktail”-type catalytic system for alkene and alkyne hydrosilylation reactions

Ondar, Evgeniia E.; Kostyukovich, Alexander Yu.; Burykina, Julia V.; Galushko, Alexey S.; Ananikov, Valentine P.

doi:10.1039/d3cy00865g

Catal. Sci. Technol.

2023

DOI: 10.1039/d3cy00865g

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Examination of Pt₂dba₃ as a “cocktail”-type catalytic system for alkene and alkyne hydrosilylation reactions

Evgeniia E. Ondar,

Alexander Yu. Kostyukovich,

Julia V. Burykina

et al.

Abstract: A simple approach aligned with dynamic catalysis principles was successfully applied in a study of hydrosilylation reactions. The readily available Pt2dba3 complex formed a “cocktail”-type system with comparable performance to known catalysts.

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2024

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Cited by 3 publications

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Prospects in Sustainable Hydrosilylation by Biphase Catalysis

Goncharova,

Beletskaya,

Arzumanyan

2024

ChemCatChem

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This concept addresses the main economic, environmental, scientific and technological issues associated with the use of homogeneous Pt‐catalysts in the important industrial hydrosilylation process. The development of biphase catalysis is proposed as the most promising approach. One solution we suggest is the use of ethylene glycol (EG) as a medium in biphase catalysis. We have previously shown that EG in Pt‐catalyzed hydrosilylation serves not only as a medium but also as a mild reducing agent of Pt‐ions to Pt0, as well as an effective ligand for the preparation of mononuclear Pt01‐complexes. These zero valent platinum complexes are single‐atom catalysts (SAC) and have high activity in hydrosilylation, stability during storage and the ability to be recycled multiple times (~40 times). This option of using an atomic catalyst allows us to combine the advantages of homogeneous and heterogeneous catalysts.

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Prospects in Sustainable Hydrosilylation by Biphase Catalysis

Goncharova,

Beletskaya,

Arzumanyan

2024

ChemCatChem

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Multi‐Catalytic Metal‐Based Homogeneous‐Heterogeneous Systems in Organic Chemistry

Arango‐Daza,

Rivero‐Crespo

2024

Chemistry A European J

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The combination of metal‐based homogeneous and heterogeneous catalysts in the same reaction media is a powerful, yet relatively unexplored approach in organic chemistry. This strategy can address important limitations associated with purely homogeneous or heterogeneous catalysis such as the incompatibility of different catalytic species in solution, or the limited tunability of solid catalysts, respectively. Moreover, the facile reusability of the solid catalyst, contributes to increase the overall sustainability of the process. As a result, this semi‐heterogeneous multi‐catalytic approach has unlocked significant advances in organic chemistry, improving existing reactions and even enabling the discovery of novel transformations, exemplified by the formal alkane metathesis. This concept article aims to showcase the benefits of this strategy through exploration of diverse relevant examples from the literature, hoping to spur research on new metal‐based homogeneous‐heterogeneous catalyst combinations that will result in reactivity challenging to achieve by conventional homogeneous or heterogeneous catalysis alone.

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Exploring Catalytic Intermediates in Pd-Catalyzed Aerobic Oxidative Amination of 1,3-Dienes: Multiple Metal Interactions of the Palladium Nanoclusters

Tabaru,

Fujihara,

Torii

et al. 2024

J. Am. Chem. Soc.

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Metal nanoclusters (NCs) have unique properties because of their small size, which makes them useful as catalysts in reactions like cross-coupling. Pd-catalyzed oxidative amination, which involves dehydrogenative C–N bond formation, uses Pd complexes as the active species. It is known that the catalytic conditions involve the formation of Pd(0) species from Pd NCs, but the precise role of Pd NCs in the transformations has not been established. In this study, we investigated the characteristic properties of Pd NCs in oxidative amination of 1,3-dienes. The reaction achieved direct amination of commercially accessible 1,3-dienes with secondary aromatic amines, providing a variety of nitrogen containing 1,3-dienes. The compound was applicable to radical polymerization to provide the nitrogen-fabricated 1,3-diene–based polymer, which exhibited a different thermal stability compared to aliphatic nitrogen-fabricated diene polymers. In addition to the synthetic utility, by combining X-ray absorption fine structure and small-angle X-ray scattering analysis, we revealed amines and 1,3-dienes affected metal leaching from the Pd nanoparticles and stabilization of Pd NCs in the catalytic reaction. Additionally, DFT calculation suggested that the catalytic intermediate contained multiple adjacent Pd atoms and was responsible for formation of an σ-allylic intermediate that is difficult to form with the use of Pd complexes. These results could be used to understand the underlying phenomenon in the oxidative coupling reaction and develop Pd NCs-based dehydrogenation.

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Examination of Pt₂dba₃ as a “cocktail”-type catalytic system for alkene and alkyne hydrosilylation reactions

Abstract: A simple approach aligned with dynamic catalysis principles was successfully applied in a study of hydrosilylation reactions. The readily available Pt2dba3 complex formed a “cocktail”-type system with comparable performance to known catalysts.

Cited by 3 publications

References 132 publications

Prospects in Sustainable Hydrosilylation by Biphase Catalysis

Prospects in Sustainable Hydrosilylation by Biphase Catalysis

Multi‐Catalytic Metal‐Based Homogeneous‐Heterogeneous Systems in Organic Chemistry

Exploring Catalytic Intermediates in Pd-Catalyzed Aerobic Oxidative Amination of 1,3-Dienes: Multiple Metal Interactions of the Palladium Nanoclusters

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Examination of Pt2dba3 as a “cocktail”-type catalytic system for alkene and alkyne hydrosilylation reactions

Abstract: A simple approach aligned with dynamic catalysis principles was successfully applied in a study of hydrosilylation reactions. The readily available Pt2dba3 complex formed a “cocktail”-type system with comparable performance to known catalysts.

Cited by 3 publications

References 132 publications

Prospects in Sustainable Hydrosilylation by Biphase Catalysis

Prospects in Sustainable Hydrosilylation by Biphase Catalysis

Multi‐Catalytic Metal‐Based Homogeneous‐Heterogeneous Systems in Organic Chemistry

Exploring Catalytic Intermediates in Pd-Catalyzed Aerobic Oxidative Amination of 1,3-Dienes: Multiple Metal Interactions of the Palladium Nanoclusters

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Product

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Examination of Pt₂dba₃ as a “cocktail”-type catalytic system for alkene and alkyne hydrosilylation reactions