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Effects of Noncovalent Interactions on the Catalytic Activity of Unsupported Colloidal Palladium Nanoparticles Stabilized with Thiolate Ligands.

ABSTRACT: This article presents the systematic evaluation of colloidal palladium nanoparticles functionalized with well-defined small organic ligands that provide spatial control of the geometric and electronic surface properties of nanoparticle catalysts. Palladium nanoparticles stabilized with thiolate ligands of different structures and functionalities (linear alkyl vs cyclohexyl vs phenyl) are synthesized using the thiosulfate protocol in a two-phase system. The structure and composition of palladium nanoparticles are characterized using transmission electron microscopy, thermogravimetric analysis, NMR, and UV-vis spectroscopies. The catalysis studies show that the chemical and structural compositions of monolayers surrounding the nanoparticle core greatly influence the overall activity and selectivity of colloidal palladium nanoparticle catalysts for the hydrogenation, isomerization, and hydrogenolysis of allylic alcohols. Especially, noncovalent interactions between surface phenyl ligands and incoming aromatic substrates are found to have a profound influence on the selectivity of colloidal palladium nanoparticles.

SUBMITTER: Maung MS

PROVIDER: S-EPMC5758047 | biostudies-literature | 2017 Sep

REPOSITORIES: biostudies-literature

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Effects of Noncovalent Interactions on the Catalytic Activity of Unsupported Colloidal Palladium Nanoparticles Stabilized with Thiolate Ligands.

Maung May S MS Shon Young-Seok YS

The journal of physical chemistry. C, Nanomaterials and interfaces 20170906 38

This article presents the systematic evaluation of colloidal palladium nanoparticles functionalized with well-defined small organic ligands that provide spatial control of the geometric and electronic surface properties of nanoparticle catalysts. Palladium nanoparticles stabilized with thiolate ligands of different structures and functionalities (linear alkyl vs cyclohexyl vs phenyl) are synthesized using the thiosulfate protocol in a two-phase system. The structure and composition of palladium ...[more]

PMID: 29326755

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Project description:Metal nanoparticle catalysts functionalized with small, well-defined organic ligands are important because such systems can provide a spatial control in the catalyst-substrate interactions. This article describes the synthesis, stability, and catalytic property evaluations of four different Pd nanoparticles capped with constitutional isomers of pentanethiolate ligands that have either a straight chain or an alkyl chain with one methyl group at different locations (α, β, or γ from the surface-bound sulfur). The structure and composition analyses of Pd nanoparticles confirm that they have similar average core sizes and organic ligand contents. The presence of methyl group at α position is found to lower the capping ability of short ligands and thus make Pd nanoparticles to lose their colloidal stability during the catalytic reactions. The overall activity and selectivity for hydrogenation and isomerization of pentene and allylbenzene derivatives are investigated for each combination of ligand and substrate. Catalysis results indicate that steric interactions between the ligands on the metal catalyst surface and the alkene substrates are a factor in controlling the activity of Pd nanoparticles. In particular, Pd nanoparticles capped with pentanethiolate isomer having a methyl group at α position exhibit poor and inconsistent catalytic activity due to its low colloidal stability. The presence of a methyl group at β position mildly interferes the adsorption of alkene group on the nanoparticle surface resulting in lower conversion yields. Interestingly, a methyl group at γ position only has a minimal effect on the catalytic property of Pd nanoparticles exhibiting similar catalysis results with Pd nanoparticles capped with straight chain pentanethiolate ligands. This indicates the proximity of steric group at the reactive site controls the nanoparticle activity for surface oriented reactions, such as hydrogenation and isomerization of alkenes in addition to their colloidal stability.

Project description:The use of more than one catalyst in one-pot reaction conditions has become a rapidly evolving protocol in the development of asymmetric catalysis. The lack of molecular insights on the mechanism and enantioselectivity in dual-catalytic reactions motivated the present study focusing on an important catalytic asymmetric Heck-Matsuda cross-coupling. A comprehensive density functional theory (M06 and B3LYP-D3) investigation of the coupling between a spirocyclic cyclopentene and 4-fluorophenyl diazonium species under a dual-catalytic condition involving Pd2(dba)3 (dba = trans, trans-dibenzylideneacetone) and chiral 2,2'-binaphthyl diamine (BINAM)-derived phosphoric acids (BDPA, 2,2'-binaphthyl diamine-derived phosphoric acids) is presented. Among various mechanistic possibilities examined, the pathway with explicit inclusion of the base (in situ generated sodium bicarbonate/sodium biphosphate) is found to be energetically more preferred over the analogous base-free routes. The chiral phosphate generated by the action of sodium carbonate on BDPA is found to remain associated with the reaction site as a counterion. The initial oxidative addition of Pd(0) to the aryl diazonium bond gives rise to a Pd-aryl intermediate, which then goes through the enantiocontrolling migratory insertion to the cyclic alkene, leading to an arylated cycloalkene intermediate. Insights on how a series of noncovalent interactions, such as C-H···O, C-H···N, C-H···F, C-H···π, lp···π, O-H···π, and C-F···π, in the enantiocontrolling transition state (TS) render the migration of the Pd-aryl to the si prochiral face of the cyclic alkene more preferred over that to the re face are utilized for modulating the enantioselectivity. Aided by molecular insights on the enantiocontrolling transition states, we predicted improved enantioselectivity from 37% to 89% by changes in the N-aryl substituents of the catalyst. Subsequent experiments in our laboratory offered very good agreement with the predicted enantioselectivities.

Dataset Information

Effects of Noncovalent Interactions on the Catalytic Activity of Unsupported Colloidal Palladium Nanoparticles Stabilized with Thiolate Ligands.

Publications

Effects of Noncovalent Interactions on the Catalytic Activity of Unsupported Colloidal Palladium Nanoparticles Stabilized with Thiolate Ligands.

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