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Article Dans Une Revue Angewandte Chemie International Edition Année : 2018

Isolation of a Reactive Tricoordinate α‐Oxo Gold Carbene Complex

Résumé

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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Chimie
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Dates et versions

hal-01678839 , version 1 (09-01-2018)

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Citer

A. Zeineddine, F. Rekhroukh, E.D. Sosacarrizo, Sonia Mallet-Ladeira, Karinne Miqueu, et al.. Isolation of a Reactive Tricoordinate α‐Oxo Gold Carbene Complex. Angewandte Chemie International Edition, 2018, 57 (5), pp.1306-1310. ⟨10.1002/anie.201711647⟩. ⟨hal-01678839⟩
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