Syntheses and ligand interconversions of copper(II) derivatives of the metalloligand [Pt2(μ-S)2(PPh3)4]

The reactivity of the metalloligand [Pt-2(mu-S)(2)(PPh3)(4)] towards a variety of copper(II)-ligand systems has been studied. Reaction of [Pt-2(mu-S)(2)(PPh3)(4)] with copper(II) halide complexes [(CuClL)-L-2] (L=2,2'-bipyridine and 1,10-phenanthroline) gave trinuclear dicationic products [Pt-2(mu-S)(2)(PPh3)(4)CuL](2+), and the 8-hydroxyquinolinate (hq) complex [Cu(hq)(2)] gave [Pt-2(mu-S)(2)(PPh3)(4)Cu(hq)](+), isolated as their BPh4- or PF6- salts. Related cationic complexes with other ancillary amine ligands (1,2-diaminoethane, 1,2-diaminopropane, 1,2-diaminocyclohexane) were obtained by reactions of [Pt-2(mu-S)(2)(PPh3)(4)] with CuCl2 and the amine. In contrast, reaction of [Pt-2(mu-S)(2)(PPh3)(4)] with CuCl2 and NH3 in methanol gave the intensely blue methoxy-bridged dicopper complex [{Pt-2(mu-S)(2)(Ph-P(3))(4)Cu(OMe)}(2)](2+), isolated as its hexa. uorophosphate salt. Copper beta-diketonate complexes reacted with [Pt-2(mu-S)(2)(PPh3)(4)] giving [Pt-2(mu-S)2(PPh3)(4)Cu(beta-diketonate)](+) PF6- complexes, with the CH3COCHCOCH3 (acac) and CF3COCHCO(2-thienyl) (tta) derivatives characterised by X-ray structure determinations. The local Cu(II) environment ranges from distorted square-planar to an intermediate form of square-planar and tetrahedral. The beta-diketonate derivatives show varying stability towards methanolysis, giving [{Pt-2(mu-S)(2)(PPh3)(4)Cu(OMe)}(2)](2+).