title: Syntheses and ligand interconversions of copper(II) derivatives of the metalloligand [Pt2(mu-S)2(PPh3)4].
abstract: The reactivity of the metalloligand [Pt2(micro-S)2(PPh3)4] towards a variety of copper(II)-ligand systems has been studied. Reaction of [Pt2(mu-S)2(PPh3)4] with copper(II) halide complexes [CuCl2L](L = 2,2'-bipyridine and 1,10-phenanthroline) gave trinuclear dicationic products [Pt2(mu-S)2(PPh3)4CuL]2+, and the 8-hydroxyquinolinate (hq) complex [Cu(hq)2] gave [Pt2(mu-S)2(PPh3)4Cu(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 [Pt2(mu-S)2(PPh3)4] with CuCl2 and the amine. In contrast, reaction of [Pt2(mu-S)2(PPh3)4] with CuCl2 and NH3 in methanol gave the intensely blue methoxy-bridged dicopper complex [{Pt(2)(mu-S)2(PPh3)4Cu(OMe)}2]2+, isolated as its hexafluorophosphate salt. Copper beta-diketonate complexes reacted with [Pt2(mu-S)2(PPh3)4] giving [Pt2(mu-S)2(PPh3)4Cu(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 [{Pt2(mu-S)2(PPh3)4Cu(OMe)}2]2+.
authors.affiliation: Department of Chemistry, University of Waikato, Private Bag 3105, Hamilton, New Zealand.
authors.forename: Sarah M
authors.initials: SM
authors.lastname: Devoy
authors.forename: William
authors.initials: W
authors.lastname: Henderson
authors.forename: Brian K
authors.initials: BK
authors.lastname: Nicholson
authors.forename: John
authors.initials: J
authors.lastname: Fawcett
authors.forename: T S Andy
authors.initials: TS
authors.lastname: Hor
mesh_terms: D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007659:Ketones / Q000737:chemistry; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D009944:Organoplatinum Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D007659:Ketones; D008024:Ligands; D009944:Organoplatinum Compounds; D003300:Copper