The complex Au(C6F5)(tht) undergoes oxidative addition when treated in solution with halogens, to give Au(C6F5)X2(tht) (X = Cl, Br or I). The tetrahydrothiophen ligand of the latter can be displaced by neutral or anionic ligands to give, respectively, the neutral complexes Au(C6F5)X2L (L = Group IVB, VB or VIB ligand) or the anionic complexes [Au(C6F5)X2X′]- (X′ = Cl or SCN).

(Pentahalophenyl) (p-tolylisocyanide)gold(I) complexes were prepared by treating Au(C6X5) (tetrahydrothiophen) (X = F, Cl or Br) with p-MeC6H4NC. Their reactivity toward nucleophiles was studied and found to decrease in the sequence: primary amines > ammonia > secondary amines > aromatic amines > alcohols; the effects of the various C6X5 groups were less pronounced, but decreased according to C6F5 > C6Cl5 > C6Br5.

The addition of isocyanide CNR (R = C6H5, tC4H9 or cyclo-C6H11) to Au(tht)(C6F5) leads to the displacement of the neutral ligand and to the formation of Au(isocyanide)(C6F5). The only hitherto known isocyanide derivatives of gold(III), Au(isocyanide) (C6F5)X2 (X = Cl, Br or I) and Au(CNC6H5)(C6F5)2Cl, have been prepared by oxidizing the obtained Au(isocyanide)(C6F5) with halogens or, respectively, Au(CNC6H5)Cl with [(C6F5)2TlBr]2.

The preparation of Pd(C6Cl5)2L2 by reacting Pd Cl2L2 with LiC6C/5 can be achieved for L being a N-, As- or S-ligand but not for L = phosphine. The As- or S- ligand can thereafter be replaced by other monoor bidentate ligands, even by phosphines.