The electrochemical oxidation of a metallic anode (zinc or cadmium) in an acetonitrile solution of a series of arenephosphinothiol ligands, 2-(Ph2P)C6H4SH, 2-(Ph2P)-6-(Me3Si)C6H3SH, 2-(Ph2PO)-6-(Me3Si)C6H3SH, and PhP(C6H4SH-2)(2) [abbreviated RP-(SH)(x), x = 1 or 2], affords [M(RP-S)(2)] and [M(RP-S-2)], M = Zn, Cd. Adducts of several of these compounds with 1,10-phenanthroline and 2,2'-bipyridine have also been obtained by addition of these coligands to the electrolysis phase. The compounds obtained have been characterized by microanalysis, IR, UV-visible, FAB spectrometry and H-1, P-31 NMR spectroscopic studies. The compounds, [Cd-2{2-(Ph2PO)C6H4S}(4)]CH3CN (1), [Zn{2-(Ph2P)-6-(Me3Si)C6H3S}(2)] (2), [Cd{2-(Ph2PO)-6-(Me3Si)C6H3S}(2)(CH3OH)] (3), and [Zn{PhPo(C6H4S-2)(2)}(bipy)] (4), have been also characterized by single-crystal X-ray diffraction. Compound 1 is binuclear with a {Cd2S2} core and distorted trigonal bipyramidal {CdO2S3} geometry about the Cd sites. Compounds 2, 3, and 4 are mononuclear with distorted tetrahedral {ZnP2S2}, distorted square pyramidal {CdO3S2}, and distorted trigonal bipyramidal {ZnON2S2} geometries, respectively. Crystal data: 1, C42H37N3O2P2S2Cd, triclinic, P (1) over bar, a = 13.5780(2) Angstrom, b = 13.8505(2) Angstrom, c = 13.9526(2) Angstrom, alpha = 105.622(1)degrees, beta = 109.693(1)degrees, gamma = 107.137(1)degrees, V = 2133.30(5) Angstrom(3), Z = 2, 9560 reflections, R = 0.0483; 2, C46H50N2P2S2Si2Zn, monoclinic, C2/c, a = 21.332(4) Angstrom, b = 9.391(2) Angstrom, c = 25.938(5) Angstrom, beta = 113.84(3)degrees, V = 4753(2) Angstrom(3), Z = 4, 2564 reflections, R = 0.0377; 3, C43H48CdO3P2S2Si2, triclinic, P (1) over bar, a = 12.1237(4) Angstrom, b = 14.0568(4) Angstrom, c = 15.0938(2) Angstrom, alpha =70.836(2)degrees, beta = 83.410(2)degrees, gamma = 65.397(2)degrees, V = 2208.7(1) Angstrom(3), Z = 2, 4936 reflections, R = 0.0738; 4, C29H22Cl3N2OP2S2Zn, triclinic, P (1) over bar, a = 8.9556(3) Angstrom, b = 12.7911(4) Angstrom, c = 14.0598(5) Angstrom, alpha = 82.671(1)degrees, beta = 73.140(1)degrees, gamma = 74.113(1)degrees, V = 1480.44(9)(1) Angstrom(3), Z = 2, 3820 reflections, R = 0.0511.