A Nucleophilic Gold(III) Carbene Complex

The [(P,P)Au=C(Ph)CO2Et]+ complex 3 [where (P,P) is an o‐carboranyl diphosphine ligand] was prepared by diazo decomposition at −40 °C. It is the first α‐oxo gold carbene complex to be characterized. Its crystallographic structure was determined and DFT calculations have been performed, unraveling the key influence of the chelating (P,P) ligand. The gold center is tricoordinate and the electrophilicity of the carbene center is decreased. Complex 3 mimics transient α‐oxo gold carbenes in a series of catalytic transformations, and provides support for the critical role of electrophilicity in the chemoselectivity of phenol functionalization (O−H vs. C−H insertion).

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Isolation of a Reactive Tricoordinate α‐Oxo Gold Carbene Complex

Zeineddine

Rekhroukh

Carrizo

et al. 2018

Angewandte Chemie

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Two Amphoteric Silver Carbene Clusters

2018

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Two highly labile silver carbene cluster complexes are described, which are unique in that they mark the transition point at which the carbene center transmutes from a fairly common NHC‐like nucleophilic behavior to an electrophilic character befitting reactive silver carbene intermediates of relevance in various catalytic transformations. This amphoteric character is the distinguishing attribute of a μ‐bridged donor/donor carbene entity that connects two silver atoms of triangular or tetrahedral metallic core units.

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(P,C) Cyclometalated Gold(III) Complexes: Highly Active Catalysts for the Hydroarylation of Alkynes

et al. 2018

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The first catalytic application of well‐defined (P,C) cyclometalated gold(III) complexes is reported. The bench‐stable bis(trifluoroacetyl) complexes 2 a,b perform very well in the intermolecular hydroarylation of alkynes. The reaction is broad in scope, it proceeds within few hours at 25 °C at catalytic loadings of 0.1–5 mol %. The electron‐rich arene adds across the C≡C bond with complete regio‐ and stereo‐selectivity. The significance of well‐defined gold(III) complexes and ligand design are highlighted in a powerful but challenging catalytic transformation.

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A Nucleophilic Gold(III) Carbene Complex

Cited by 13 publications

References 67 publications

Isolation of a Reactive Tricoordinate α‐Oxo Gold Carbene Complex

Isolation of a Reactive Tricoordinate α‐Oxo Gold Carbene Complex

Two Amphoteric Silver Carbene Clusters

(P,C) Cyclometalated Gold(III) Complexes: Highly Active Catalysts for the Hydroarylation of Alkynes

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