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

Treatment of gold(III) pincer complexes ((CNC)-N-boolean AND-C-boolean AND)*AuX with trifluoroacetic acid (X = C6F5, thiophenyl, Me, Et) or of ((CNC)-N-boolean AND-C-boolean AND)*AuOAcF with AgOAcF/arylboronic acids leads to the selective cleavage of a C-Au bond under mild conditions to give the bidentate complexes (HC-(CN)-N-boolean AND)*Au(X)(OAcF) [((CNC)-N-boolean AND-C-boolean AND)* = 2,6-(C6H3But)(2)pyridine]. Alkylation of ((CNC)-N-boolean AND-C-boolean AND)*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-(CN)-N-boolean AND)*Au(C6H4F)(OAcF) is about an order of magnitude more intense than that of its tridentate parent compound.