Synthesis and Structural Characterization of Neutral Silver(I) Complexes with Arenephosphinothiols. Crystal Structures of [Ag₄{2-(Ph₂P)-6-(Me₃Si)C₆H₆S}₄] and [Ag₄{2-(Ph₂PO)-6-(Me₃Si)C₆H₃S}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.

The use of sacrificial anodes for the electrochemical synthesis of metallic complexes

“…The new chloride ligand in the metal coordination sphere seems to come from the non-innocent solvent, CH 2 Cl 2 , as previously mentioned [252][253][254]. The structure of the complex [Ni 2 (L86) 3 Cl] is similar to that reported for the analogous cobalt [Co 2 (L86) 3 4 ] complex was obtained [257]. In this case the monoanionic oxophosphanylthiolato ligands act as binuclear triple bridges.…”

“…The molecular structures of the complexes [Cu 2 (L7a) 2 (dppe)] and [Cu 2 (L7a) 2 (dppm)] are similar and show that the copper atoms are joined by a double thiolato bridge which involves two different monoanionic phosphanylthiolato ligands that chelates one copper and bridges the other metal through the sulfur atom.The anodic oxidations of zinc and cadmium anodes were also reported as successful procedures for the syntheses of the corresponding M(II) complexes with P-S donor ligands[258]. So, the electrolysis of acetonitrile solutions of HL7 and HL84b yielded the corresponding[M(L) 2 ] complexes, with the ligand exhibiting a bidentate monoanionic behavior, as reported for [Zn(L7b) 2 ].…”

Coordination chemistry of the main group elements with phosphine, arsine and stibine ligands

“…In solution, 31 tetrahedral geometry with chelating 3-diphenylphosphinopropyl groups [55]. Electrochemical oxidation of a zinc anode in MeCN solutions of various phosphinothiols (o-C 6 H 4 (PPh 2 )SH, o-C 6 H 3 (Me 3 Si)(PPh 2 )SH or PhP(o-C 6 H 4 SH) 2 ) gave the Zn(II) complexes of the phosphinothiolate anions [56].…”

Dimeric Silver(I) Complex: Bis(dipropyldithiophosphato) bis(1,10-phenanthroline) Disilver(I); Dimeric Silver(I) Complex: Bis(dipropyldithiophosphato) bis(1,10-phenanthroline) Disilver(I);Ag2[Phen]2[S2P(OPr)2]2

“…[12][13][14] Similarly, no significant difference of the Ag-S bond distances [2.559(1) and 2.567(1) Å] is observed compared with those of similar tetrahedral structure [2.507~2.644 Å]. 5,15 The highest value for the tetrahedral angles is N(1)-Ag-S(1) [127.71 (9) o ]; which is 19 o greater than the ideal value. The lowest value is N(1)-Ag-N(2) [68.9 (1) o ], which is 40 o lower than the idea value.…”

“…Theses features are the result of the tendency of thiolate ligands to bridge metal centers to yield oligomeric (I) : ( ) (1,10-) or polymeric species. 5 On the other hand, the presence of coligands, such as 2,2-bipyridine, 1,10-phenanthroline, bis(diphenylphosphino)methane, etc, might modify such aggregation processes producing binuclear or polynuclear thiolate complexes. 6 When 1,10-phenanthroline reacts with bis(dipropyldithiophosphato) silver(I) in EtOH, we obtained a new dinuclear silver(I) complex, bis(1,10-phenanthroline) bis(dipropy ldithiophosphato) disilver(I).…”