Novel Pentacyano Complexes of Tri- and Tetravalent Platinum

New pentacyano complexes of tri- and tetravalent platinum were obtained in aqueous solution and characterized by multinuclear NMR ((195)Pt, (13)C) supported by Raman spectroscopy. The complexes form as products of redox decomposition of metal-metal bonded platinum-thallium compounds. The trimetallic [(NC)(5)Pt-Tl-Pt(CN)(5)](3)(-) yields a new dimeric compound of Pt(III), [(NC)(5)Pt-Pt(CN)(5)](4)(-). The latter is a rare representative of unbridged dimeric complexes of trivalent platinum; it was obtained through an oxidation of monomeric square-planar platinum(II) species by a metal complex. From the bimetallic compounds [(NC)(5)Pt-Tl(CN)(n)()](n)()(-) (n = 0-2) tetravalent platinum complexes are formed. Depending on the Pt-Tl species, electron transfer is initiated either by heat or by exposition to light; it results in [Pt(CN)(6)](2)(-) or in the hitherto unknown complexes [Pt(CN)(5)(OH)](2)(-) and [Pt(CN)(5)(H(2)O)](-), with the (195)Pt NMR chemical shift values 1638.7 (+/-0.6) and 1766.7 (+/-0.6), respectively. Proton dissociation constant of [Pt(CN)(5)(H(2)O)](-) has been determined, pK(a) = 2.51 (+/-0.01). In both Pt(III) and Pt(IV) pentacyano complexes platinum is hexacoordinated forming a pseudo-octahedron with two types of cyano ligands: four equivalent equatorial cyanides and one apical. Related platinum(IV) species, [Pt(CN)(5)X](2)(-) (X = Cl, Br, I), have also been studied. In all the pentacyano complexes a pronounced trans influence is reflected in a substantial difference between the (195)Pt-(13)C spin-spin coupling constant for the apical (trans) and the equatorial (cis) carbon sites. In this respect, the studied X ligands can be ordered in a series of decreasing (195)Pt-(13)C(trans) coupling constant: H(2)O > Cl(-) > Br(-) > I(-) > OH(-) > CN(-).