Addition of bis(diphenylphosphino)amine (dppa) to neutral or cationic gold(I) and gold(III) complexes containing weakly co-ordinating neutral ligands leads to the formation of complexes of the following types: [RAu(dppa)AuR], [Au₂(dppa)₂][ClO₄]₂, [AuR₃(dppa)], and [AuR₂Cl(dppa)](R = C₆F₆ or C₆Cl₅). Oxidative-addition of halogens X₂(X = Cl or Br) to the gold(I) complexes leads to the gold(II) derivatives [RXAu(dppa)AuXR] and [XAu(dppa)₂AuX][ClO₄]₂ which can be further arylated with Ag(C₆F₅) to give [R₂Au(dppa)AuR₂] and [RAu(dppa)AuR][ClO₄]₂. Mixed gold(III)–gold(I) derivatives can also be synthesized either by the spontaneous isomerization of the gold(II) complexes or from mononuclear gold(III) derivatives. The structure of the complex [(C₆F₅)ClAu(dppa)AuCl(C₆F₅)] has been determined by single-crystal X-ray diffraction: space group C₂/c, a= 18.009(3), b= 17.033(2), c= 18.420(3)Å, β= 103.79(2)°, Z= 4, and R= 0.035 for 4 000 unique observed reflections. The molecule possesses crystallographic two-fold symmetry, with Au–Au 2.576(2)Å; this is the shortest reported Au–Au bond. The unit cell also contains eight di-isopropyl ether and four water molecules, which are well ordered and form a hydrogen bonding network with the amine N-H group.