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 = C6F5, thiophenyl, Me, Et) or of (C∧N∧C)*AuOAcF with AgOAcF/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)­(OAcF) [(C∧N∧C)* = 2,6-(C6H3But)2pyridine]. Alkylation of (C∧N∧C)*Au­(OAcF) with AlR3 (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(C6H4F)­(OAcF) is about an order of magnitude more intense than that of its tridentate parent compound.