COMPLEXES WITH PT-H-AG BONDS

Silver ions react with 2 equiv of the hydrides trans-[PtH(C6X5)(PR3)2] (X = F and Cl, R = Me and Et; X = H, R = Et) to give trinuclear complex cations of the type [(PR3)2(C6X5)Pt(mu-H)Ag(A-H)Pt(C6X5)(PR3)2]+ which were characterized by multinuclear NMR spectroscopy. A full report of the X-ray crystal structure of [(PEt3)2(C6Cl5)Pt(mu-H)Ag(mu-H)Pt-(C6Cl5)(PEt3)2](CF3SO3) is also given. The silver ion in this complex is linear with two hydride ligands, the H-Ag-H angle being ca. 152-degrees. Significant Pt...Ag direct interactions are also likely to occur. Crystal data: space group P1BAR, a = 13.853 (3) angstrom,b = 14.214 (2) angstrom, c = 15.611 (3) angstrom, alpha = 94.64 (2)degrees, beta = 90.48 (2)degrees, gamma = 110.39 (2)degrees, Z = 2, V = 2869.7 angstrom3, rho(calcd) = 1.875 g cm-3, R = 0.049. The reaction of AgCF3SO3 and trans-[PtH(C6Cl5)(PEt3)2], in a 1:1 ratio, gave the complex [(PEt3)2(C6Cl5)Pt(mu-H)Ag(H2O)](CF3SO3), which was characterized by multinuclear NMR spectroscopy and by X-ray and neutron diffraction. Also in this complex, the silver ion is linearly coordinated. Here, however, it is bonded to one hydride ligand and to one water molecule. Crystal data (neutron, 24 K): space group P1BAR, a = 8.581 (2) angstrom, b = 12.053 (3) angstrom, c = 15.519 (3) angstrom, alpha = 87.86 (2)degrees, beta = 73.55 (2)degrees, gamma = 81.76 (2)degrees, Z = 2, V = 1523 angstrom3, rho(calcd) = 2.105 g cm-3, R(F2) = 0.081.