Synthesis and structural characterization of neutral silver(I) complexes with arenephosphinothiols. Crystal structures of [Ag₄{2-(Ph₂P)-6-(Me₃Si)C₆H ₆S}₄] and [Ag₄{2-(Ph₂PO)-6-(Me₃Si)C₆H ₃S}₄]

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, ¹H, ¹³C, and ³¹P NMR) methods, and ligand 3 and [Ag₄{2-(Ph₂P)-6-(Me₃Si)C₆H ₃S}₄] (5) and [Ag₄{2-(Ph₂PO)-6-(Me₃Si)C₆H ₃S}₄] (6) complexes were characterized by X-ray crystallographic techniques. Crystal data for 3: C₂₁H₂₃OPSSi, monoclinic, P2(1)/n, a = 11.3730(4) Å, b = 11.1562(4) Å,c= 17.1153(6) Å, β = 103.961(1)°, V = 2107.4(1) ų, Z = 4, 2730 reflections with I_o > 2σ(I_o), R = 0.0621. Crystal data for 5: C₈₄H₈₈Ag₄P₄S₄Si ₄, tetragonal, P4(2)2(1)2, a = 18.8454(7) Å, b= 18.8454(7) Å, c = 24.596(2) Å, V = 8735.1(7) ų, Z = 4, 4676 reflections with I_o > 2σ(I_o), R = 0.0286. Crystal data for 6: C₉₀H₉₇Ag₄N₃O₄P ₄S₄Si₄, trigonal, P1, a = 13.4567(1) Å, b= 14.4148(2) Å, c = 14.8080(2) Å, a = 99.130(1)°, β = 98.815(1)°, g = 114.211(1)°, V = 2509.38(5) ų, Z = 1, 6345 reflections with I_o > 2σ(I_o), R = 0.0505. The [Ag₄{2-(Ph₂P)-6-(Me₃Si)C₆H ₃S}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 [Ag₄(2-(Ph₂PO)-6-(Me₃Si)C₆H ₃S}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.