Gold/Palladium Bimetallic Nanoclusters for C-X Bond Activation: A Unique Effect of Gold

Dhital, Raghu Nath; Ehara, Masahiro; Sakurai, Hidehiro

doi:10.5059/yukigoseikyokaishi.73.1130

Cited by 5 publications

(9 citation statements)

References 63 publications

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“…[386,387] However,t he absence of this process during the chemisorption of bromoarenes led to slow kinetics for the Ullmann coupling but energetically favorable routesf or Suzuki-Miyaura-type cross-coupling reactions. An initial studys uggested that during the activation of chemisorbedc hloroarenes on the Au/Pd catalyst, the leachingo f Pd 2 + assisted by Au contributed to the favorable kinetics for the Ullmann coupling.…”

Section: Heterogeneous Synergistic and Bimetallic Au Catalysis For Thmentioning

confidence: 99%

“…The mechanisms of Ullmann coupling of chloroarenes by Au 0.5 Pd 0.5 :PVP alloys and the unique halogen dependence have been the subject of experimental and computational studies. An initial study suggested that during the activation of chemisorbed chloroarenes on the Au/Pd catalyst, the leaching of Pd 2+ assisted by Au contributed to the favorable kinetics for the Ullmann coupling . However, the absence of this process during the chemisorption of bromoarenes led to slow kinetics for the Ullmann coupling but energetically favorable routes for Suzuki–Miyaura‐type cross‐coupling reactions.…”

Section: Heterogeneous Au Catalysis For Homocoupling and Cross‐couplimentioning

confidence: 99%

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Gold‐Catalyzed Cross‐Coupling Reactions: An Overview of Design Strategies, Mechanistic Studies, and Applications

Nijamudheen

Datta

2019

Chemistry A European J

152

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Transition-metal-catalyzed cross-couplingr eactions are central to many organic synthesis methodologies. Traditionally,P d, Ni, Cu, and Fe catalysts are used to promote these reactions. Recently,m any studies have showedt hat both homogeneous and heterogeneous Au catalysts can be used for activating selective cross-coupling reactions.H ere, an overview of the past studies, current trends, andf uture directions in the field of gold-catalyzed coupling reactions is presented.D esign strategiest oa ccomplish selective homocoupling and cross-coupling reactions under both homogeneous and heterogeneous conditions, computational and ex-perimental mechanistic studies, and their applicationsi nd iverse fields are critically reviewed. Specific topics covered are:o xidant-assisted and oxidant-free reactions;s train-assisted reactions;d ual Au and photoredoxc atalysis;b imetallic synergistic reactions;m echanismso fr eductivee limination processes;e nzyme-mimicking Au chemistry;c lustera nd surface reactions;a nd plasmonic catalysis. In the relevant sections, theoretical and computational studies of Au I /Au III chemistry are discussed and the predictionsf rom the calculationsa re compared with the experimental observations to derive useful design strategies.A. Nijamudheen earnedh is PhD from IACS, Kolkata,i n2 015. Currently,h ei sapostdoctoral researcher atF loridaS tate University.H is researchi nterests are in computational catalysis, solar energym aterials, and beyond Li-ion battery technologies.Ayan Dattai sc urrently aP rofessor at IACS, Kolkata.H is research interests include theoretical and computational studieso ft ransitionmetal-catalyzed reactions,o pto-electronic properties of organic and solid-statem aterials, and the design of renewableenergymaterials. He has won several awards including the DST-SERB Distinguished Investigator Award (DIA) in 2019.

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Section: Heterogeneous Synergistic and Bimetallic Au Catalysis For Thmentioning

confidence: 99%

Section: Heterogeneous Au Catalysis For Homocoupling and Cross‐couplimentioning

confidence: 99%

Gold‐Catalyzed Cross‐Coupling Reactions: An Overview of Design Strategies, Mechanistic Studies, and Applications

Nijamudheen

Datta

2019

Chemistry A European J

152

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“…The inverse halogen dependence of the reaction was also well interpreted by the leaching process of a solvated Pd complex. 22,23 Recently, an efficient and durable Au/Pd NC catalyst has been developed using ion-exchange resin support. 24 However, the entire reaction mechanism of this reaction has not been fully understood because there are a couple of possible routes, a combination of some elemental steps and the surrounding effects, which should be examined in detail for this complex coupling reaction.…”

Section: Introductionmentioning

confidence: 99%

Mechanism of Ullmann Coupling Reaction of Chloroarene on Au/Pd Alloy Nanocluster: A DFT Study

et al. 2016

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Recently, a unique catalytic system of bimetallic Au/Pd alloy nanoclusters (NCs) for Ullmann coupling of chloroarenes (ArCl), which works at low temperature in high yield, has been developed (J. Am. Chem. Soc. 2012, 134, 20250). In this work, the full catalytic cycle of this reaction has been investigated for ArCl, producing biphenyl on the Au/Pd alloy NCs by DFT calculations with the M06-L functional. Two possible reaction pathways are proposed, namely, (i) ArCl oxidative addition followed by Cl abstraction from the NC surface occurs twice stepwise and (ii) the successive oxidative addition of two ArCl proceeds before the Cl abstraction. Both of these pathways are energetically possible, and in the latter case, the Cl atoms stay on the NC surface. The exothermic reaction pathways were obtained for this multistep reaction scheme. The rate-determining step was shown to be hydrogen transfer from dimethylformamide (DMF), which is consistent with the experimental isotope effect observation. The proton shuttle mediated by water considerably reduces the activation barrier. The side reaction, which produces benzene via hydrogenation, is prohibited by the second ArCl oxidative addition. The present study has revealed the essential mechanism of the coupling reaction on supported Au/Pd NC catalysts, suggesting that the entire reaction is controlled by several factors including the surroundings and solvents. These findings provide useful insights for the further developments of efficient NC catalysts through designing the supports, interface, and reaction conditions.

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“…As noted in introduction, the yield of the present reaction on Au−Pd NC catalyst drastically reduces for other hydrides which are usually used in coupling reactions. For example, yield was 48 % for ArBr in the same reaction condition and even the reaction never proceeded in the case of ArI; namely, the inverse halogen dependence was observed ,. To elucidate the origin of this dependence, the oxidative addition of ArBr on Au 10 Pd 10 NC was examined in the presence of aqueous solution by the DFT calculations .…”

Section: Resultsmentioning

confidence: 99%

“…Although the reaction proceeds for aryl chloride (ArCl) in high yield over 90 % for various substrates, the reaction yield is drastically reduced for aryl bromide (ArBr) and the reaction does not even proceed for aryl iodide (ArI); namely, the inverse halogen dependence was observed in this system ,. Later, an efficient and durable Au−Pd NC catalyst has been developed using ion‐exchange resin support .…”

Section: Introductionmentioning

confidence: 99%

Gold‐Palladium Nanocluster Catalysts for Homocoupling: Electronic Structure and Interface Dynamics

Ehara

2019

The Chemical Record

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The gold‐palladium (Au−Pd) bimetallic nanocluster (NC) catalyst in colloidal phase performs the homocoupling reaction of various aryl chlorides (Ar−Cl) under ambient conditions. We have systematically investigated various aspects of the Au−Pd NC catalysts with respect to this homocoupling reaction by using density functional theory (DFT) calculations, genetic algorithm (GA) approaches, and molecular dynamics (MD) simulations. Our findings include the geometric and electronic structures of the Au−Pd NC, the reactive Pd sites on the NC surface, the electron‐donating effects of surrounding polymer matrix, the reaction mechanism of homocoupling reaction and rate‐determining step, the inverse halogen dependence of the reaction, and the solvation dynamics at interface region between NC and polymer matrix in aqueous solution.

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Gold/Palladium Bimetallic Nanoclusters for C-X Bond Activation: A Unique Effect of Gold

Cited by 5 publications

References 63 publications

Gold‐Catalyzed Cross‐Coupling Reactions: An Overview of Design Strategies, Mechanistic Studies, and Applications

Gold‐Catalyzed Cross‐Coupling Reactions: An Overview of Design Strategies, Mechanistic Studies, and Applications

Mechanism of Ullmann Coupling Reaction of Chloroarene on Au/Pd Alloy Nanocluster: A DFT Study

Gold‐Palladium Nanocluster Catalysts for Homocoupling: Electronic Structure and Interface Dynamics

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