Premium
Isolation of a Reactive Tricoordinate α‐Oxo Gold Carbene Complex
Author(s) -
Zeineddine Abdallah,
Rekhroukh Feriel,
Sosa Carrizo E. Daiann,
MalletLadeira Sonia,
Miqueu Karinne,
Amgoune Abderrahmane,
Bourissou Didier
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201711647
Subject(s) - carbene , ligand (biochemistry) , chemistry , electrophile , chemoselectivity , diazo , reactivity (psychology) , stereochemistry , medicinal chemistry , catalysis , organic chemistry , medicine , biochemistry , receptor , alternative medicine , pathology
The [(P,P)Au=C(Ph)CO 2 Et] + 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).