The synthesis of the first series of 4-mono and 3,5-bis(dimethylamino)methyl-functionalized triarylphosphanes of the general formula PPh 3 À n Ar n (Ar = 1-C 6 H 3 (CH 2 NMe 2 ) 2 -3,5 (NC(H)N), n = 1 (ligand 2) or n = 3 (ligand 4); Ar = 1-C 6 H 4 (CH 2 NMe 2 )-4 (NC(H)), n = 3 (ligand 7)) is described. These phosphanes were used for the construction of complexes of the form [AuCl(P)] and [PtCl 2 (P) 2 ]. In these complexes selective coordination of phosphorus to the metal ion is observed. The 31 P NMR data show the formation of cis-Pt complexes, even in the case of triarylphosphane 4, which features a tris{3,5-bis(dimethylamino)methyl} substitution pattern. The structure of the gold complex of mono-3,5-functionalized triarylphosphane 2 in the solid state shows a striking resemblance to the structure of the corresponding complex [AuCl(PPh 3 )]. The solid-state structure of the AuCl complex of tris-4-functionalized ligand 7 differs from that of [AuCl(PPh 3 )] in the sign of the torsion angles. The amine functionalities in this class of gold compounds could be reacted selectively with either acid (HCl, H 3 PO 4 ) to generate ammonium salts or with an alkylating agent (benzyl bromide) to afford benzyl ammonium salts, without the violation of the Au-P bond.