Bi- and trinuclear platinum-silver complexes with or without platinum-silver bonds. Molecular structure of [PPh3(C6Cl5)ClPt(.mu.-Cl)AgPPh3]

When (NBu4)2[trans-PtCl2(C6Cl 5)2] is reacted with O3ClOAgL (L = PPh3, PEt3; molar ratio 1:1), the binuclear (NBu4)[PtAgCl2(C6Cl5)2L] (L = PPh3 (I), PEt3 (II)) complexes are obtained, while, for L = PPh2Me, the trinuclear [Pt(C6Cl5)2{(μ-Cl)AgL}2] (III) is obtained in low yield. The trinuclear complexes with L = PPh2Me (III, in higher yield), L = PPh3 (IV), and L = PEt3 (V) are obtained when the above-mentioned reactions are carried out in a 1:2 molar ratio. (NBu4)[trans-PtCl2(C6Cl5)L] reacts with O3ClOAgL′ (molar ratio 1:1 or 1:2), yielding the novel binuclear derivatives [L(C6Cl5)ClPt(μ-Cl)AgL′] (L′ = PPh3, L = PPh3 (VI), SC4H8 (VII), NC5H5 (VIII); L′ = PPh2Me, L = PPh3 (IX)). The structure of VI has been solved by single-crystal X-ray diffraction. The compound crystallizes in the monoclinic system, space group P21/n, with a = 14.270 (2) Å, b = 14.663 (2) Å, c = 20.024 (2) Å, β = 93.58 (1)°, V = 4181.69 Å3, and Z = 4. The structure was refined to residuals of R = 0.037 and Rw = 0.037. The >PtCl2(C6Cl5)PPh3> and >AgPPh3> fragments are bonded by a single chlorine bridge, Pt(μ-Cl)Ag (Pt-Cl1 = 2.341 (3) Å, Ag-Cl1 = 2.514 (2) Å), and a weak Pt-Ag bond (Pt-Ag = 2.945 (1) Å), and two [(PPh3)(C6Cl5)ClPt(μ-Cl)Ag(PPh3)] units are connected through a weak Ag′-Cl1 interaction (Ag′⋯Cl1 = 3.023 (2) Å). The silver atom makes a short contact with one o-chlorine atom of the C6Cl5 groups (Ag⋯C17 = 3.041 (4) Å). © 1989 American Chemical Society.We gratefully acknowledge the Dirección General de Investigación Científica y Técnica for financial support (Project PB 85-0128) and for research grants (to LA. and J.M.C.).Peer Reviewe