SYNTHESIS AND REACTIVITY OF A NEW CLASS OF NEUTRAL POLYMERIC COMPLEXES [PTAGX2(C6CL5)L]X - CRYSTAL-STRUCTURE OF [PTAGCL2(C6CL5)PPH3]X.1.5XCH2CL2

Reacting (NBu4)[trans-PtX2(C6Cl5)L] (X = Cl, L = PPh3, SC4H8, p-MeC6H4NH2, NC5H5; X = Br, L = PPh3) with AgClO4 in 1:1 molar ratio leads to the polymeric complexes [PtAgX2(C6Cl5)L]x (X = Cl, L = PPh3 (1), SC4H8 (2), p-MeC6H4NH2 (3), NC5H5 (4); X = Br, L = PPh3 (5)). The structure of complex 1 has been solved by single-crystal X-ray diffraction. The compound crystallizes in the orthorhombic system, space group Pna2(1) with a = 10.327(3) angstrom, b = 18.094(6) angstrom, c = 18.451(5) angstrom, V = 3447.69 angstrom3, and Z = 4. The structure was refined to residuals of R = 0.0414 and R(w) = 0.0492. Each repeat unit is formed by the interaction of the square planar fragment [trans-PtCl2(C6Cl5)PPh3]- with Ag+ via a Pt-Ag bond (Pt-Ag = 2.855(2) angstrom) which is supported by a Pt(mu-Cl(2))Ag bridge. These units are connected by a Pt(mu-Cl(1))Ag bridging system, resulting in the formation of the polymer. The silver atom also makes a short contact with one o-Cl atom of the C6Cl5 group (o-Cl...Ag = 2.838(6) angstrom). Complex 1 reacts with PPh3 (1:1) to give [PPh3(C6Cl5)ClPt(mu-Cl)AgPPh3], but the reaction with SC4H8 results in the elimination of AgCl and formation of [PtCl(C6Cl5)PPh3(SC4H8)].