Direct Ag-Pt-2 interactions in pentafluorophenyl A-frame complexes containing halide or OH- and bis(diphenylphosphino)methane (dppm) as bridging ligands. Crystal structures of [(C6F5)(2)Pt(mu-OH)(mu-dppm){Ag(PPh(3))}Pt(C6F5)(2)]center dot C7H8 and [(C6F5)(2)Pt(mu-SC4H8)(mu-dppm)Pt(C6F5)(2)]center dot 1/2C(6)H(14)

Complexes [NBu(4)][(C6F5)(2)Pt(mu-X)(mu-dppm)Pt(C6F5)(2)] (X = Cl, Pr) react with AgClO4 and [Ag(OClO3)L] (L = PPh(3), SC4H8), yielding different compounds depending on the silver reagent used. The reactions with AgClO4 in wet solvents lead to the syntheses of the complexes [(C6F5)(2)Pt(mu-X)(mu-dppm){Ag(H2O)}Pt(C6F5)(2)] [X = Cl (1), Pr (2)] in which the existence of two Pt-Ag bonds is postulated. The reactions with [Ag(OClO3)(PPh(3))] give similar complexes [(C6F5)(2)Pt(mu-X)(mu-dppm){Ag(PPh(3))}Pt(C6F5)(2)] [X = Cl (3), Br(4)]. The presence of silver coordinated to the platinum atoms activates the substitution of the halogen bridge; thus, 3 reacts with water, yielding the complex [(C6F5)(2)Pt(mu-OH)(mu-dppm){Ag(PPh(3))}Pt(C6F5)(2)] (5). Complex 5 can be prepared as well by reaction of [NBu(4)][(C6F5)(2)Pt(mu-OH)(mu-dppm)Pt(C6F5)(2)] (6) With [Ag(OClO3)(PPh(3))]. Nevertheless, the reaction of [NBu(4)][(C6F5)(2)Pt(mu-Cl)(mu-dppm)Pt(C6F5)(2)] with the complex [Ag(OClO3)(SC4H8)] does not render the analogous complex to 3, but AgCl precipitates and [(C6F5)(2)Pt(mu-SC4H8)(mu-dppm)Pt(C6F5)(2)] (7) is formed. This different behavior depending on the ligand present in the silver complex is probably due to the ability of the tetrahydrothiophene ligand to act as a bridge. Single-crystal X-ray studies of 5 and 7 have been carried out. For 5, the existence of two Pt-Ag bonds with distances 2.791(1) and 2.832(1) Angstrom has been confirmed. Complex 7 shows a distorted six-membered ring skeleton formed by the metal atoms, dppm ligand, and sulfur atom of the SC4H8 group. Compound 5 . C7H8 (C74H46AgF20OP3Pt2) crystallizes in the monoclinic system, space group P2(1)/n: a = 14.360(1) Angstrom, b = 21.590(1) Angstrom, c = 21.585(2) Angstrom, beta = 90.85(1)degrees, V = 6691.3(8) Angstrom(3), Z = 4. Compound 7 . 1/2C(6)H(14) (C56H37F20P2Pt2S) crystallizes in the monoclinic system, space group P2(1)/n: a = 22.258(6) Angstrom, b = 11.351(3) Angstrom, c = 22.268(5) Angstrom, beta = 106.21(3)degrees, V = 5402.6(16) Angstrom(3), Z = 4.