New mixed metal chain complexes of platinum(II) with copper(II), cobalt(II), nickel(II), zinc(II), uranium(VI), and thorium(IV) having substituted phosphonito groups as bridging ligands

Abstract

Complexes PtCl(OP(OMe)/sub 2/)(HOP(OMe)/sub 2/)L (L = PEt/sub 3/, PPh/sub 3/) are acidic and the proton bonded to oxygen can be removed by titration with sodium methoxide or 1,5-diazabicyclo(4.3.0)non-5-ene. The resulting anionic compound will chelate to copper(II), cobalt(II), dioxouranium(VI), and thorium(IV) through the oxygens to give mixed metal compounds (PtCl(OP(OR)/sub 2/)/sub 2/L)/sub n/M (n = 2, R = Me, L = PEt/sub 3/, M = Cu, UO/sub 2/ and L = PPh/sub 3/, M = Co; n = 2, R = Ph, L = PEt/sub 3/, M = Cu; n = 4, R = Me, L = PPh/sub 3/, M = Th). The complex PtCl(OP(OMe)/sub 2/)(F/sub 2/BOP(OMe)/sub 2/)PEt/sub 3/ can be prepared by treating PtCl(OP(OMe)/sub 2/)(HOP(OMe)/sub 2/)PEt/sub 3/ with BF/sub 3/ . Et/sub 2/O. Mixed metal trimetallic compounds are also obtained by treating the compounds Pt(OP(OMe)/sub 2/)/sub 2/(L--L) with the appropriate metal salt (L--L = 1,2-bis(diphenylphosphino)ethane (dppe), o-phenylenebis(dimethylarsine)(diars)). Complexes ((Pt(OP(OMe)/sub 2/)/sub 2/(L--L))/sub 2/M)(ClO/sub 4/)/sub 2/ (M = Cu, Zn, L--L = dppe, diars; M = Ni, Co, L--L = dppe) have been prepared. Electronic spectra of the mixed metal complexes show a square-planar geometry about copper (II) and nickel(II) and a tetrahedral geometry about cobalt(II). The cobalt(II) complexes show unusually lowmore » extinction coefficients for the visible and near-infrared bands, although with Racah parameter B values in the 650--700-cm/sup -1/ range the explanation for the low extinction coefficients is likely distortion rather than highly ionic character about Co(II).« less