Silver complexes of the anionic forms of 2-(diphenylphosphino)benzenethiol [2-(Ph2P)C6H4SH] (1), 2-(diphenylphosphino)-6-(trimethylsilyl)benzenethiol [2-(Ph2P)-6-(Me3Si)C6H3SH] (2), and 2-(diphenylphosphinyl)-6-(trimethylsilyl)benzenethiol, [2-(Ph2PO)-6-(Me3Si)C6H3SH] (3) have been prepared by an electrochemical procedure and characterized by spectroscopic (IR, H-1, C-13, and P-31 NMR) methods, and ligand 3 and [Ag-4{2-(Ph2P)-6-(Me3Si)C6H3S}(4)] (5) and [Ag-4{2-(Ph2PO)-6-(Me3Si)C6H3S}(4)] (6) complexes were characterized by X-ray crystallographic techniques. Crystal data for 3 : C21H23OPSSi, monoclinic, P2(1)/n, a = 11.3730(4) Angstrom, b = 11.1562(4) Angstrom, c = 17.1153(6) Angstrom, beta = 103.961(1)degrees, V = 2107.4(1) Angstrom(3), Z = 4, 2730 reflections with I-0 > 2 sigma(I-0), R = 0.0621. Crystal data for 5 : C84H88Ag4P4S4Si4, tetragonal, P4(2)2(1)2, a = 18.8454(7) Angstrom, b = 18.8454(7) Angstrom, c = 24.596(2) Angstrom, V = 8735.1(7) Angstrom(3), Z = 4, 4676 reflections with I-0 > 2 sigma(I-0), R = 0.0286. Crystal data for 6 : C90H97Ag4N3O4P4S4Si4, trigonal, P1, a = 13.4567(1) Angstrom, b = 14.4148(2) Angstrom, c = 14.8080(2) Angstrom, alpha = 99.130(1)degrees, beta = 98.815(1)degrees, g = 114.211(1)degrees, V = 2509.38(5) Angstrom(3), Z = 1, 6345 reflections with I-0 > 2 sigma(I-0), R = 0.0505. The [Ag-4{2-(Ph2P)-6-(Me3Si)C6H3S}(4)] (5) compound is tetranuclear with an array of four silver atoms bridged by four sulfur atoms. Each silver atom has a distorted trigonal [AgS2P] environment with each ligand acting as P,S bidentate S-bridging ligand. The [Ag-4(2-(Ph2PO)-6-(Me3Si)C6H3S}(4)] (6) complex is also tetranuclear, but in this case two of the silver atoms are [AgO2S2] tetracoordinated and the other two Ag atoms are [AgS2] two coordinated.