Zwitterionic Mixed‐Carbene Coinage Metal Complexes: Synthesis, Structures, and Photophysical Studies

Chotard, Florian; Romanov, Alexander S.; Hughes, David L.; Linnolahti, Mikko; Bochmann, Manfred

doi:10.1002/ejic.201900573

Cited by 20 publications

(19 citation statements)

References 69 publications

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“…Reactions of these anionic NHCs with transition metals afford corresponding zwitterionic complexes. Anionic, six-membered ring NHCs based on a malonate unit (maloNHC), introduced by Cesar, Lavigne and co-workers [30], are particularly interesting as they are attractive ligands to stabilize late transition metal ion complexes such as those involving Ag I , Au I , Rh I , Cu I [30][31][32][33][34][35], as well as Fe II [36].…”

Section: Introductionmentioning

confidence: 99%

Mercury(II) Complexes of Anionic N-Heterocyclic Carbene Ligands: Steric Effects of the Backbone Substituent

2020

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Mercury(II) complexes (Me-maloNHCDipp)HgCl (1b), (t-Bu-maloNHCDipp)HgCl (2b) and (t-Bu-maloNHCDipp)HgMe (2c) supported by anionic N-heterocyclic carbenes have been obtained in good yields from the reaction of the potassium salt of N-heterocyclic carbene ligand precursors and mercury(II) salts, HgCl2 and MeHgI. These molecules have been characterized by 1H-NMR, 13C-NMR and IR spectroscopy and elemental analysis. X-ray crystal structures of 1b and 2b are also presented. Interestingly, complex 1b is polymeric {(Me-maloNHCDipp)HgCl}n in the solid state, as a result of inter-molecular Hg-O contacts, and features rare three coordinate mercury sites with a T-shaped arrangement, whereas the (t-Bu-maloNHCDipp)HgCl (2b) is monomeric and has a linear, two-coordinate mercury center. The formation of T-shaped structure and the aggregation of complex 1b is attributable to the reduced steric demand of the N-heterocyclic carbene ligand backbone substituent.

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Section: Introductionmentioning

confidence: 99%

Mercury(II) Complexes of Anionic N-Heterocyclic Carbene Ligands: Steric Effects of the Backbone Substituent

2020

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“…224 As highlighted across several reports, the quantum yield in (CAAC)CuCl complexes is directly linked to the steric environment provided by the ligand in the order 13b 225 > 13e 225,226 > 13f, 226,227 and is a consequence of the increased rigidity of the system. Moreover, these reports underline for the first time the unique zwitterionic mix-carbene 91, 229 all resulting in distinct changes in photophysical behavior. It is worth mentioning that the introduction of flexible electron-rich N-donors such as the formamidinato 86 extends the photophysical properties toward the development of power-efficient white organic light-emitting diode (WOLEDs).…”

Section: Optoelectronic Applications Of Cyclic (Alkyl)(amino)carbene Coinage Metal Complexesmentioning

confidence: 85%

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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“…27 We have previously employed the selected methodology with success for closely related molecules. 28,29 Overlap integrals and HOMO-LUMO centroid distances have been calculated using Multiwfn program. 30 All calculations were carried out by Gaussian…”

Section: Synthesis Of (5-methyl-33-diphenyl-1-(p-tolyl)-3h-indolizin-2-ylidene)gold(i) Chloride (1)mentioning

confidence: 99%

Synthesis and photophysical properties of linear gold(i) complexes based on a CCC carbene

2021

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Zwitterionic Mixed‐Carbene Coinage Metal Complexes: Synthesis, Structures, and Photophysical Studies

Cited by 20 publications

References 69 publications

Mercury(II) Complexes of Anionic N-Heterocyclic Carbene Ligands: Steric Effects of the Backbone Substituent

Mercury(II) Complexes of Anionic N-Heterocyclic Carbene Ligands: Steric Effects of the Backbone Substituent

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

Synthesis and photophysical properties of linear gold(i) complexes based on a CCC carbene

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