Trinuclear Gold Clusters Supported by Cyclic (alkyl)(amino)carbene Ligands: Mimics for Gold Heterogeneous Catalysts

Jin, Liqun; Weinberger, David S.; Melaïmi, Mohand; Moore, Curtis E.; Rheingold, Arnold L.; Bertrand, Guy

doi:10.1002/ange.201404665

Cited by 74 publications

(7 citation statements)

References 105 publications

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“…Therefore, the preparation of the smallest possible clusters, namely tris(gold) clusters, was attempted. 86 Note that before this work, there was only one example of such a small cluster, namely the NHC supported cluster 39 reported by Sadighi et al 87 (Scheme 11). Small phosphinesupported gold clusters are usually prepared by reduction of µ3-oxo complexes [(R3PAu)3O] + X -42.…”

Section: Synthesis Of Caac-coinage Metal Clustersmentioning

confidence: 79%

“…This striking discovery led to the question of whether very small, well-defined clusters, capped with ligands, such as 40-43 (Scheme 11), could also behave as efficient catalysts. 86 To tackle this question, the carbonylation of amines, which is the simplest and most environmentally friendly route for the preparation of urea derivatives, 182 was chosen. It was found that 2.5 mol% of trinuclear gold complex 41e catalyzed the carbonylation of cyclohexylamine under 30 psi of CO and 10 psi of O2.…”

Section: Trinuclear (Caac) Gold Clusters As Catalysts For the Carbonylation Of Aminesmentioning

confidence: 99%

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Cyclic (Alkyl)- and (Aryl)-(amino)carbene Coinage Metal Complexes and Their Applications

2020

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Cyclic (alkyl)-and (aryl)-(amino)carbenes (CAACs and CAArCs) are stronger sdonors and p-acceptors than imidazol-2-ylidenes and imidazolidin-2-ylidenes, the well-known Nheterocyclic carbenes (NHCs). Consequently, they form strong bonds with coinage metals, and stabilize both low and high oxidation states. This Focus Review shows that CAACs and CAArCs have allowed for the isolation of copper and gold complexes which were believed to be only transient intermediates. This has not only allowed for a better understanding of the mechanism of known processes but has also led to the development of novel coinage metal-catalyzed reactions.In addition to their role in homogeneous catalysis, CAAC and CAArC coinage metal complexes have recently found applications in medicinal chemistry, as well as in materials science. When possible, the performance of CAAC and CAArC ligands are compared with those of classical NHCs. 2 CONTENTS 1. Introduction 2. Coordination Chemistry of Cyclic (Alkyl)-and (Aryl)-(Amino)carbenes with Coinage Metals 2.1. Synthesis of (CAAC)MCl (M = Cu, Ag, Au) Complexes 2.2. Synthesis of Various Gold(I) and Gold(III) Complexes from (CAAC)AuCl and (CAAC)AuOH 2.3. Synthesis of (CAAC)CuH Complexes 2.4. Synthesis of CAAC Coinage Metal Alkene, Alkyne, and Aryl p-Complexes 2.5. Synthesis of CAAC Coinage Metal PCO Complexes 2.6. Synthesis of CAAC Coinage Metal(0) Complexes 2.7. Synthesis of CAAC Coinage Metal Clusters 2.8. Synthesis of HemilabileCAAC-Gold(I) and (III) Complexes. Oxidative addition at Gold(I) 2.9. Coordination Chemistry of CAAC-6 and BiCAAC 2.10. Synthesis of Saturated Abnormal Carbene and Cyclic (Aryl)(amino)carbene Coinage Metal Complexes 3. Cyclic (Alkyl)(Amino)carbene Coinage Metal Complexes in Catalysis 3.1. Catalytic Cross-Coupling of Two Unsaturated Carbon Centers Leading to Allenes 3.2. Gold Catalyzed Hydroamination of Alkynes and Allenes, and Hydroammoniumation and Methylamination of Alkynes3.3. (CAAC)-Mono-and -Bis-(copper)acetylide Complexes in Catalysis. 3.4. (CAAC) Coinage Metals for the Activation of Small Molecules 3.4.1. (CAAC)CuBH4 Complexes for the Catalytic Hydrolytic Dehydrogenation of BH3NH3 and for the Reduction of CO2 into Formate with H2. 3.4.2. Trinuclear (CAAC) Gold Clusters as Catalysts for the Carbonylation of Amines 3.5. Miscellaneous 3.5.1. (CAAC) Gold and Copper Catalysts for the Hydroarylation of Styrene with Anilines 3.5.2. (CAAC)Gold(I) Complexes in Gold/Palladium Dual Catalysis 3.5.3. (CAAC) Gold(III) Complexes in Migratory Insertion of Carbenes into Au(III)-C Bonds. 3.6. Chiral CAAC Ligands in Enantioselective Catalysis 4. Biological Applications of Cyclic (Alkyl)-and (Aryl)-(Amino)carbene Coinage Metal Complexes 5. Optoelectronic Applications of Cyclic (Alkyl)(amino)carbene Coinage Metal Complexes 6.

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Section: Synthesis Of Caac-coinage Metal Clustersmentioning

confidence: 79%

Section: Trinuclear (Caac) Gold Clusters As Catalysts For the Carbonylation Of Aminesmentioning

confidence: 99%

Cyclic (Alkyl)- and (Aryl)-(amino)carbene Coinage Metal Complexes and Their Applications

2020

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“…The reactivity of [P(µ-NTer)] 2 (1) (Ter = 2,6-dimesityl-phenyl) has been utilized widely to activate small molecules such alkenes and alkynes leading to bicycles and cages compounds. [18][19][20] Here we want to report on the activation of a phosphaalkyne, P≡C-t Bu, [21][22][23][24] its rearrangement reaction to a [2.1.1]heterobicycles (2, Scheme 2) and its application in gold(I) complexation reactions (Scheme 3).…”

Section: Resultsmentioning

confidence: 99%

“…However, complex chemistry of gold recently has put forth astonishing examples like Bertrand's cAAC-stabilized gold(0) and gold(I) complexes and trinuclear clusters. [1][2][3] The coordination of phosphaalkynes to gold(I) was investigated by Russell et al (Scheme 1), who observed side-on coordination of the P-C unit as the preferred bonding mode (A) 4 and the s-coordination of (PC t Bu) 3 to a Au-NHC complex (B). 5 Furthermore, Weigand et al were able to elegantly demonstrate the coordination of a phosphanide up to two AuCl moieties (C).…”

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confidence: 99%

P–P σ-bond activation by gold(I) coordination

2015

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Bond activation by gold is of imminent interest with respect to catalytic activity. By coordination of an AuCl fragment onto the P-P σ-bond of an azadiphosphiridine, the P-P bond is cleaved to give a PNP type of ligand in the gold(I) complex. Another equivalent of the gold precursor selectively binds on a P lone pair. The bonding situation was further studied by means of computation, indicating the existence of a 3-center-2-electron bond.

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“…In recent reports, this class of ligands were successfully introduced in clusters [22]. Several works on gold NCs, such as Au3 [25,26], Au11 [27], Au13 [28,29], Au25 [30], and Au44 [31], demonstrated that NHCs could endow them with exciting stability, luminescence and reactivity. NHC-stabilized Ag and Cu clusters have also been prepared, in which no hydride was observed [32][33][34][35][36][37].…”

Section: Introductionmentioning

confidence: 99%

Copper-hydride nanoclusters with enhanced stability by N-heterocyclic carbenes

et al. 2021

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Copper-hydrides have been intensively studied for a long time due to their utilization in a variety of technologically important chemical transformations. Nevertheless, poor stability of the species severely hinders its isolation, storage and operation, which is worse for nano-sized ones. We report here an unprecedented strategy to access to ultrastable copper-hydride nanoclusters (NCs), namely, using bidentate N-heterocyclic carbenes as stabilizing ligands in addition to thiolates. In this work, a simple synthetic protocol was developed to synthesize the first large copper-hydride nanoclusters (NCs) stabilized by N-heterocyclic carbenes (NHCs). The NC, with the formula of Cu31(RS)25(NHC)3H6 (NHC = 1,4-bis(1-benzyl-1H-benzimidazol-1-ium-3-yl) butane, RS = 4-fluorothiophenol), was fully characterized by high resolution Fourier transform ion cyclotron resonance mass spectrum, nuclear magnetic resonance, ultra-violet visible spectroscopy, density functional theory (DFT) calculations and single-crystal X-ray crystallography. Structurally, the title cluster exhibits unprecedented Cu4 tetrahedron-based vertex-sharing (TBVS) superstructure (fusion of six Cu4 tetrahedra). Moreover, the ultrahigh thermal stability renders the cluster a model system to highlight the power of NHCs (even other carbenes) in controlling geometrical, electronic and surface structure of polyhydrido copper clusters.

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Trinuclear Gold Clusters Supported by Cyclic (alkyl)(amino)carbene Ligands: Mimics for Gold Heterogeneous Catalysts

Cited by 74 publications

References 105 publications

Cyclic (Alkyl)- and (Aryl)-(amino)carbene Coinage Metal Complexes and Their Applications

Cyclic (Alkyl)- and (Aryl)-(amino)carbene Coinage Metal Complexes and Their Applications

P–P σ-bond activation by gold(I) coordination

Copper-hydride nanoclusters with enhanced stability by N-heterocyclic carbenes

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