The First Gold(III) Formate: Evidence for β‐Hydride Elimination

Kumar, Roopender; Krieger, Jean‐Philippe; Gómez‐Bengoa, Enrique; Fox, Thomas; Linden, Anthony; Nevado, Cristina

doi:10.1002/ange.201705557

Cited by 16 publications

(2 citation statements)

References 77 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The β‐hydride elimination could be a key step leading to the major products or side reactions during several late transition‐metal‐catalyzed reactions. For Au catalysis, β‐hydride elimination has only rarely been reported . Based on all the early results and hypotheses, achieving Au‐catalyzed selective cross‐coupling reactions was considered a nontrivial task.…”

Section: Introductionmentioning

confidence: 99%

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

Nijamudheen

Datta

2019

Chemistry A European J

145

View full text Add to dashboard Cite

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.

show abstract

Section: Introductionmentioning

confidence: 99%

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

Nijamudheen

Datta

2019

Chemistry A European J

145

View full text Add to dashboard Cite

show abstract

“…The molecular structure of 5 was confirmed by X‐ray crystallography (Figure ). The Au−O bond distance in the Au I formate 5 of 2.140(4) Å is slightly longer than that of a reported Au III formate (2.102 Å) . To the best of our knowledge, the formation of 5 represents the first example of any gold formate obtained by direct hydroauration of CO 2 .…”

Section: Methodsmentioning

confidence: 65%

NHC‐Coordinated Diphosphene‐Stabilized Gold(I) Hydride and Its Reversible Conversion to Gold(I) Formate with CO₂

et al. 2019

View full text Add to dashboard Cite

An NHC-coordinated diphosphene is employed as ligand for the synthesis of ah ydrocarbon-soluble monomeric Au I hydride,w hichr eadily adds CO 2 at room temperature yielding the corresponding Au I formate.T he reversible reaction can be expedited by the addition of NHC,whichinduces bhydride shift and the removal of CO 2 from equilibrium through the formation of an NHC-CO 2 adduct. The Au I formate is alternatively formed by dehydrogenative coupling of the Au I hydride with formic acid (HCO 2 H), thus in total establishing areaction sequence for the Au I hydride mediated dehydrogenation of HCO 2 Ha sc hemical hydrogen storage material.Tertiary phosphines I (Scheme 1) are ubiquitous ligands and thus play an important role in the organometallic chemistry of transition metals [1] and thereby also in the area of homoge-nous catalysis. [2] Celebrated examples of the use of phosphines include Wilkinsonscatalyst, [3] Noyoriscatalyst, [4] and the first generation Grubbs catalyst. [5] Other phosphorusbased species such as diphosphenes II [6] and base-stabilized phosphinidenes III [7] (Scheme 1) have also found applications as ligands in transition-metal complexes.

show abstract

κ³‐(N^C^C)Gold(III) Carboxylates: Evidence for Decarbonylation Processes

et al. 2019

Self Cite

View full text Add to dashboard Cite

Gold(III) carboxylate species, stabilized by a κ3‐(N^C^C) ligand template, are presented herein. A η1‐AuIII‐C(O)‐OH species has been characterized under cryogenic conditions as a result of the nucleophilic attack of an ammonium hydroxide onto a dinuclear μ‐CO2‐κ3‐(N^C^C)AuIII precursor. Thermal decomposition for these species proceeds by an unusual decarbonylation process, in contrast to typical decarboxylation pathways observed in related metallocarboxylic acids.

show abstract

The First Gold(III) Formate: Evidence for β‐Hydride Elimination

Abstract: The first stable gold(III) formate and experimental evidence for its b-hydride elimination are described. Acatalytic dehydrogenation of formic acid together with mechanistic studies shed light on potential pathways operating in fundamental gold-catalyzed transformations.

Cited by 16 publications

References 77 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

NHC‐Coordinated Diphosphene‐Stabilized Gold(I) Hydride and Its Reversible Conversion to Gold(I) Formate with CO₂

κ³‐(N^C^C)Gold(III) Carboxylates: Evidence for Decarbonylation Processes

Contact Info

Product

Resources

About

The First Gold(III) Formate: Evidence for β‐Hydride Elimination

Abstract: The first stable gold(III) formate and experimental evidence for its b-hydride elimination are described. Acatalytic dehydrogenation of formic acid together with mechanistic studies shed light on potential pathways operating in fundamental gold-catalyzed transformations.

Cited by 16 publications

References 77 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

NHC‐Coordinated Diphosphene‐Stabilized Gold(I) Hydride and Its Reversible Conversion to Gold(I) Formate with CO2

κ3‐(N^C^C)Gold(III) Carboxylates: Evidence for Decarbonylation Processes

Contact Info

Product

Resources

About

NHC‐Coordinated Diphosphene‐Stabilized Gold(I) Hydride and Its Reversible Conversion to Gold(I) Formate with CO₂

κ³‐(N^C^C)Gold(III) Carboxylates: Evidence for Decarbonylation Processes