Syntheses and ligand interconversions of copper(II) derivatives of the metalloligand [Pt2(mu-S)2(PPh3)4].
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+.
Devoy
Sarah M
SM
Department of Chemistry, University of Waikato, Private Bag 3105, Hamilton, New Zealand.
Henderson
William
W
Nicholson
Brian K
BK
Fawcett
John
J
Hor
T S Andy
TS
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
D007659:Ketones; D008024:Ligands; D009944:Organoplatinum Compounds; D003300:Copper