Selective Au–C Cleavage in (C ∧ N ∧ C)Au(III) Aryl and Alkyl Pincer Complexes

Treatment of gold(III) pincer complexes (C ∧ N ∧ C)*AuX with trifluoroacetic acid (X = C 6 F 5, thiophenyl, Me, Et) or of (C ∧ N ∧ C)*AuOAc F with AgOAc F /arylboronic acids leads to the selective cleavage of a C–Au bond under mild conditions to give the bidentate complexes (HC-C ∧ N)*Au(X)(OAc F ) [(C ∧ N ∧ C)* = 2,6-(C 6 H 3 Bu t ) 2 pyridine]. Alkylation of (C ∧ N ∧ C)*Au(OAc F ) with AlR 3 (R = Me, Et) proved to be a high-yielding route to gold(III) alkyls. Au–C cleavage significantly influences reactivity, e.g., with boronic acids. The photoemission of the cleavage product (HC-C ∧ N)*Au(C 6 H 4 F)(OAc F ) is about an order of magnitude more intense than that of its tridentate parent compound.