The synthesis of some Au(I) aryldithiocarboxylates (ArPh, o-tolyl, p-tolyl) and their 1:1 and 1:2 complexes with triphenylphosphine are reported and their properties are compared with those of the corresponding Cu(I) and Ag(I) derivatives. Variable temperature 1H and 13C NMR solution spectra of the phosphino complexes are discussed and show a particularly strong metal-phosphine interaction in the [Au(S 2CAr)PPh 3] molecules, which are fairly stable in solution. [Au(S 2CAr)(PPh 3) 2] are stable in solution only below −30 °C. Approximate constants for the equilibria [Au(S 2CAr)(PPh 3) 2]⇌[Au(S 2CAr)PPh 3]+PPh 3 are reported. The intermolecular exchange of the phosphine between the mono and the bisphosphino complexes is fast and that between the latter and free phosphine even faster. Crystal and molecular structures have been determined by standard X-ray methods for the [Au(S 2CPh)PPh 3] ( I), [Au(S 2CPh)(PPh 3) 2] ( II) and [(Au,Cu)S 2C- p-tolyl(PPh 3) 2] ( III) complexes. In I there are two independent monomeric units in both of which the dithiobenzoate is monodentate, the metal atoms being coordinated by the ligands in a linear geometry. The gold atom in II and the cocrystallized copper/gold atoms in III are pseudo-tetrahedrally coordinated by the two PPh 3 and the chelating aryldithiocarboxylate anion. The four-membered chelate ring in II shows a remarkably long AuS bond (2.859(4) Å). The coordination number of gold(I) and the strain involved in the formation of chelate rings with gold are discussed. Crystallographic data are as follows: C 25H 20AuPS 2 ( I), monoclinic, space group P2 1/ n, with a=19.952(4), b=12.733(4), c=19.894(4) Å, β=117.74(2)° and Z=8; C 43H 35AuP 2S 2 ( II), monoclinic, space group P2 1/ n, with a=20.712(3), b=19.552(2), c=9.180(2) Å, β=98.54(1)° and Z=4; C 44H 37Au 0.56Cu 0.44P 2S 2 ( III), orthorhombic, space group P2 12 12 1, with a=20.492(2), b=15.823(2), c=11.980(2) Å and Z=4. The structures, solved by Patterson and Fourier methods, were refined by blocked full matrix least-squares to R=0.068 ( I), 0.044 ( II) and 0.034 ( III) for 3503 ( I), 3242 ( II) and 3273 ( III) symmetry independent reflections.