A simple access to transition metal cyclopropenylidene complexes

Bidal, Yannick D.; Lesieur, Mathieu; Melaïmi, Mohand; Cordes, David B.; Slawin, Alexandra M. Z.; Bertrand, Guy; Cazin, Catherine S. J.

doi:10.1039/c4cc10375k

Cited by 38 publications

(36 citation statements)

References 62 publications

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“…The results are compared with those obtained with the [Cu(Cl)(SIMes)] 1 CuCl ,15a,26b,27 and the recently reported [Cu(Cl)(BAC)] 5 CuCl (Figure 3). 28 Three different substrate sets were chosen. The reactions were conducted at room temperature, without solvent, and using 0.5 mol% of catalyst loading.…”

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confidence: 99%

Copper(I) Complexes Bearing Carbenes Beyond Classical N‐Heterocyclic Carbenes: Synthesis and Catalytic Activity in “Click Chemistry”

et al. 2015

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Thes ynthesis andc haracterization of abnormal N-heterocyclic carbene,c yclic (alkyl)(amino)carbene,a nd mesoionic carbene copper(I) complexesa re reported.T hese organometallic species are obtained via aversatile and inexpensive synthetic pathwayu sing readily available reactants,n amely copper oxide andi miniums alts.T he catalytic activity of this series of complexes was evaluated in the [3+ +2] cycloaddition of alkynes with azides (CuAAC). Outstanding catalytic properties were observed for the abnormal NHC-a nd triazolylidenebased copper(I) complexes.

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Section: Resultsmentioning

confidence: 99%

Copper(I) Complexes Bearing Carbenes Beyond Classical N‐Heterocyclic Carbenes: Synthesis and Catalytic Activity in “Click Chemistry”

et al. 2015

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“…8 A second major class of carbocyclic carbenes is represented by the cycloheptatrienylidenes (CHTs), the first examples of which were reported in 1978 by Jones et al 9 In 2006 Bertrand et al succeeded in the isolation of the first free cyclopropenylidene derivative, 10 but in contrast to the isolation of the first free NHC by Arduengo in 1991 11 this did not prompt a comparable breakthrough, although some studies suggested that carbocyclic carbene ligands have similar potential in catalysis. [12][13][14] The lag in their development also shows up in the fact that only within the last two years the first Au-CHT complex 15 and a Cu-based transmetallation agent for cyclopropenylidene ligands 16 were reported -landmarks long established in NHC chemistry. 3 Like the NHCs, CHTs and cyclopropenylidenes act mainly as s-donors with only minor backbonding and all three classes generally feature similar M-C carbene bond lengths.…”

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“…The chemical shift of the carbocyclic carbene-C appears considerably more downfield than that of the NHC: 185. 16 (in the solid state). However, this is still a tremendous upfield-shift compared to literature-known Pd complexes of isolated CHT-ligands, for which carbene resonances have been reported in a region of ca.…”

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A hybrid carbocyclic/N-heterocyclic carbene ligand

Jandl

Pöthig

2017

Chem. Commun.

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We report the synthesis and characterisation of the first complex bearing a bidentate carbocyclic/N-heterocyclic carbene ligand, which represents an unprecedented combination of these two carbene classes. Starting from an unsubstituted cycloheptatrienylidene-Pd complex, the ligand was built up in an on-site synthesis at the metal center. DFT calculations were employed to understand the crucial allyl-to-alkyl rearrangement of the carbocycle in this sequence and all its binding modes during the reaction cascade were crystallographically characterised.

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“…26,27 Note that all these gold, silver and copper complexes can be prepared by simple addition at room temperature of the free carbene 1 to Au(SMe2)Cl, AgCl and CuCl, respectively. Alternatively, following the seminal discovery by Lin et al 28 on the ability of Ag(I)-NHC complexes to transfer Ag-bound NHC ligands to another metal, both the silver 10 25 and even the copper complexes 13 29 can undergo a transmetallation to give the desired CAACcoinage metal complexes.…”

Section: Synthesis Of (Caac)mcl (M = Cu Ag Au) Complexesmentioning

confidence: 99%

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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A simple access to transition metal cyclopropenylidene complexes

Abstract: We report the first example of BAC-Cu complex (BAC = bis(diisopropylamino)cyclopropenylidene) and its use as a carbene-transfer reagent, allowing access to Au-, Pd-, Ir-and Rh-BAC compounds. Catalytic experiments show the high activity of the [CuCl(BAC)] complex in Click chemistry.

Cited by 38 publications

References 62 publications

Copper(I) Complexes Bearing Carbenes Beyond Classical N‐Heterocyclic Carbenes: Synthesis and Catalytic Activity in “Click Chemistry”

Copper(I) Complexes Bearing Carbenes Beyond Classical N‐Heterocyclic Carbenes: Synthesis and Catalytic Activity in “Click Chemistry”

A hybrid carbocyclic/N-heterocyclic carbene ligand

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

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