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Stabilization of Nanoparticles Produced by Hydrogenation of Palladium-N-Heterocyclic Carbene Complexes on the Surface of Graphene and Implications in Catalysis.

ABSTRACT: Palladium nanoparticles (NPs) have been obtained by decomposition of well-defined palladium complexes noncovalently anchored onto the surface of reduced graphene oxide. Morphological analysis by microscopy showed the presence of small palladium NPs homogeneously distributed on the support. Characterization by X-ray photoelectron spectroscopy confirmed that palladium NPs contain Pd(2+) and Pd(0) oxidation states and the presence of N-heterocyclic carbene and bromo ligands. The catalytic properties of the NPs with and without the support have been evaluated in the hydrogenation of alkynes. Supported palladium NPs showed increased activity versus the nonsupported ones and could be recycled up to 10 times without the loss of catalytic activity. The composition of the palladium NPs is different for each catalytic cycle indicating a dynamic process and the formation of different catalytic active species. On the contrary, the unsupported palladium NPs showed limited activity caused by decomposition and could not be recycled. The role of the support has been investigated. The results indicate that the support influences the stability of palladium NPs.

SUBMITTER: Mollar-Cuni A

PROVIDER: S-EPMC6643925 | biostudies-literature |

REPOSITORIES: biostudies-literature

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A Cooperative N-Heterocyclic Carbene/Palladium Catalysis System.

Project description:N-heterocyclic carbenes (NHC) have been extensively studied as organocatalysts and ligands for transition metals, but the successful integration of NHCs and late transition metals in cooperative catalysis remains an underexplored area. We have developed a cooperative palladium-catalyzed allylation of NHC-activated aldehydes to access a variety of 3-allyl dihydrocoumarin derivatives. Kinetic experiments support a cooperative pathway for this transformation.

| S-EPMC4212655 | biostudies-literature

N-Heterocyclic Carbene Bound Nickel(I) Complexes and Their Roles in Catalysis.

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| S-EPMC3092490 | biostudies-literature

A family of N-heterocyclic carbene-stabilized borenium ions for metal-free imine hydrogenation catalysis.

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| S-EPMC3838997 | biostudies-literature

Transfer Hydrogenation of Ketones Catalyzed by Symmetric Imino-N-heterocyclic Carbene Co(III) Complexes.

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| S-EPMC7033672 | biostudies-literature

Aryl radical-mediated N-heterocyclic carbene catalysis.

Project description:There have been significant advancements in radical reactions using organocatalysts in modern organic synthesis. Recently, NHC-catalyzed radical reactions initiated by single electron transfer processes have been actively studied. However, the reported examples have been limited to catalysis mediated by alkyl radicals. In this article, the NHC organocatalysis mediated by aryl radicals has been achieved. The enolate form of the Breslow intermediate derived from an aldehyde and thiazolium-type NHC in the presence of a base undergoes single electron transfer to an aryl iodide, providing an aryl radical. The catalytically generated aryl radical could be exploited as an arylating reagent for radical relay-type arylacylation of styrenes and as a hydrogen atom abstraction reagent for α-amino C(sp3)-H acylation of secondary amides.

| S-EPMC8219674 | biostudies-literature

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Project description:Tetrahydrothiophene-functionalized N,S-heterocyclic carbene palladium(II) complexes are synthesized through an unexpected rearrangement that proceeds with palladium(II) trifluoroacetate and not with palladium(II) acetate, palladium(II) bromide, or palladium(II) chloride. A series of these complexes were isolated and characterized by X-ray crystallography. The mechanism of formation of these [3.2.1]-palladabicycles was explored, and the catalytic capabilities of these complexes were demonstrated in representative C-C coupling reactions.

| S-EPMC8382225 | biostudies-literature

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Project description:The enantioselective construction of C-CF2R (R: alkyl or fluoroalkyl) bonds has attracted the attention of synthetic chemists because of the importance of chiral fluorinated compounds in life and materials sciences. Catalytic asymmetric fluoroalkylation has mainly been realized under organocatalysis and Lewis acid catalysis, with substrates limited to carbonyl compounds. Few examples using transition-metal catalysis exist, owing to side reactions including decomposition and isomerization of fluoroalkylating reagents. Herein we report umpolung asymmetric difluoroallylation of hydrazones with 3-bromo-3,3-difluoropropene (BDFP) under palladium catalysis. Difluoroallylation products having quaternary chiral carbon centers are afforded in good yields with high α/γ- and enantioselectivities. The usefulness of the reaction products is demonstrated and an inner-sphere mechanism of the reaction is proposed. The use of chiral N-heterocyclic carbene as ligand is the key for the selectivities as well as the productivity of the reaction.

| S-EPMC8589859 | biostudies-literature

Palladium carbene complexes as persistent radicals.

Project description:A series of palladium(ii) radical carbene complexes, [PC˙(sp2)P]PdI, [PC˙(sp2)P]PdBr, and [PC˙(sp2)P]PdCl (PC(sp3)H2P = bis[2-(di-iso-propylphosphino)-phenyl]methane), is described. Compound [PC˙(sp2)P]PdI dimerizes to {[PC(sp2)P]PdI}2 in the solid state, akin to the formation of Gomberg's dimer. While the bromo and the iodo derivatives could be obtained from the oxidation of [PC(sp2)P]Pd(PMe3) by the respective dihalogens, a halogen transfer reaction from CH2Cl2 was used for the formation of [PC˙(sp2)P]PdCl. The halogen transfer from CH2X2 (X = Cl, Br, I) could be used to obtain all three radical carbene palladium complexes and also allowed the isolation of [PC(CH2)P]Pd(PMe3), which is the result of methylene group transfer from CH2X2. Compound [PC(CH2)P]Pd(PMe3) was independently synthesized from [PC(CH3)HP]PdCl2, which contains a supporting ligand analogous to that of the radical carbene complexes but has one of the hydrogen atoms replaced by a methyl group. All three carbene radical species abstract a hydrogen from 9,10-dihydroanthracene or n Bu3SnH.

| S-EPMC5500858 | biostudies-literature

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