Syntheses and NMR spectroscopic ivestigations of salts containing the novel anions [PtXn(CF3)6-n]2- (n=0-5, X = F, OH, Cl, CN) and crystal structure of K2[(CF3)2F2Pt(μ-OH)2PtF2(CF3)2]•2H2O

The first syntheses of trifluoromethyl-complexes of platinum through fluorination of cyanoplatinates are reported. The fluorination of tetracyanoplatinates(II), K-2[Pt(CN)(4)], and hexacyanoplatinates(IV), K-2[Pt(CN)(6)], with CIF in anhydrous HF leads after working up of the products to K-2[(CF3)(2)F2Pt(mu-OH)(2)PtF2(CF3)(2)].2H(2)O. The structure of the salt is determined by a X-ray structure analysis, P2(1)/c (Nr. 14), a = 11.391(2), b = 11.565(2), c = 13.391(3) Angstrom, beta = 90.32(3)degrees, Z = 4, R-1 = 0.0326 (I > 2sigma(I)). The reaction of [Bu4N](2)[Pt(CN)(4)] with CIF in CH2Cl2 generates mainly cis-[Bu4N](2)[PtCl2(CF3)(4)] and fac-[Bu4N](2)[PtCl3(CF3)(3)], but in contrast that of [Bu4N](2)[Pt(CN)(6)] with CIF in CH2Cl2 results cis-[Bu4N](2)[PtX2(CF3)(4)], [Bu4N](2)[PtX(CF3)(5)] (X = F, Cl) and [Bu4N](2)[Pt(CF3)(6)]. In the products [Bu4N](2)[PtXn(CF3)(6-n)] (X = F, Cl, n = 0-3) it is possibel to exchange the fluoroligands into chloro- and cyano-ligands by treatment with (CH3)(3)SiCl and (CH3)(3)SiCN at 50 degreesC. With continuing warming the trifluoromethyl-ligands are exchanged by chloro- and cyanoligands, while as intermediates CF2Cl and CF2CN ligands are formed. The identity of the new trifluoromethyl-platinates is proved by Pt-195- and F-19-NMR-spectroscopy.