The reaction between [Me 2 AuCl] 2 and the lithium salt of a β-diketimine, [HC{C(Me)N(C 6 H 3 -2, 6-Me 2 )} 2 Li], yields the neutral Au(III) compound [HC{C(Me)N(C 6 H 3 -2,6-Me 2 )} 2 AuMe 2 ] (1). Compound 1 reacts with 1 equiv of triflic acid (HOTf) at -78 °C to provide the cationic AuTreatment of 1 with 2 equiv of HOTf results in the displacement of Me 2 AuOTf and formation of the β-diketiminato triflate salt [HC{C(Me)NH(C 6 H 3 -2,6-Me 2 )} 2 ][OTf] (3). Compound 1 reacts with I 2 to yield the cation [HC(I)-{C(Me)N(C 6 H 3 -2,6-Me 2 )} 2 AuMe 2 ] þ , which is isolated as the triflate salt [HC(I){C(Me)N(C 6 H 3 -2,6-Me 2 )} 2 AuMe 2 ][OTf] ( 4). The reaction of 1 with (PPh 3 )AuCl in the presence of AgOTf provides [HC(AuPPh 3 ){C(Me)N(C 6 H 3 -2,6-Me 2 )} 2 AuMe 2 ][OTf] (5). Molecular structures of 1, 4, and 5 were elucidated by single-crystal X-ray diffraction experiments; that of 4 was additionally confirmed by quantum-chemical calculations. The reactivity experiments indicate that the methine carbon in the β-diketiminato unit of 1 is the exclusive site of electrophilic attack, while the Au-C bonds are not perturbed.