Synthesis and Structural Characterization of Neutral Silver(I) Complexes with Arenephosphinothiols. Crystal Structures of [Ag(4){2-(Ph(2)P)-6-(Me(3)Si)C(6)H(6)S}(4)] and [Ag(4){2-(Ph(2)PO)-6-(Me(3)Si)C(6)H(3)S}(4)

Abstract

Silver complexes of the anionic forms of 2-(diphenylphosphino)benzenethiol [2-(Ph(2)P)C(6)H(4)SH] (1), 2-(diphenylphosphino)-6-(trimethylsilyl)benzenethiol [2-(Ph(2)P)-6-(Me(3)Si)C(6)H(3)SH] (2), and 2-(diphenylphosphinyl)-6-(trimethylsilyl)benzenethiol [2-(Ph(2)PO)-6-(Me(3)Si)C(6)H(3)SH] (3) have been prepared by an electrochemical procedure and characterized by spectroscopic (IR, (1)H, (13)C, and (31)P NMR) methods, and ligand 3 and [Ag(4){2-(Ph(2)P)-6-(Me(3)Si)C(6)H(3)S}(4)] (5) and [Ag(4){2-(Ph(2)PO)-6-(Me(3)Si)C(6)H(3)S}(4)] (6) complexes were characterized by X-ray crystallographic techniques. Crystal data for 3: C(21)H(23)OPSSi, monoclinic, P2(1)/n, a = 11.3730(4) Å, b = 11.1562(4) Å, c = 17.1153(6) Å, beta = 103.961(1) degrees, V = 2107.4(1) Å(3), Z = 4, 2730 reflections with I(o) > 2sigma(I(o)), R = 0.0621. Crystal data for 5: C(84)H(88)Ag(4)P(4)S(4)Si(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) Å(3), Z = 4, 4676 reflections with I(o) > 2sigma(I(o)), R = 0.0286. Crystal data for 6: C(90)H(97)Ag(4)N(3)O(4)P(4)S(4)Si(4), trigonal, P1, a = 13.4567(1) Å, b = 14.4148(2) Å, c = 14.8080(2) Å, alpha = 99.130(1) degrees, beta = 98.815(1) degrees, g = 114.211(1) degrees, V = 2509.38(5) Å(3), Z = 1, 6345 reflections with I(o) > 2sigma(I(o)), R = 0.0505. The [Ag(4){2-(Ph(2)P)-6-(Me(3)Si)C(6)H(3)S}(4)] (5) compound is tetranuclear with an array of four silver atoms bridged by four sulfur atoms. Each silver atom has a distorted trigonal [AgS(2)P] environment with each ligand acting as P,S bidentate S-bridging ligand. The [Ag(4)(2-(Ph(2)PO)-6-(Me(3)Si)C(6)H(3)S}(4)] (6) complex is also tetranuclear, but in this case two of the silver atoms are [AgO(2)S(2)] tetracoordinated and the other two Ag atoms are [AgS(2)] two coordinated.