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

Abstract
The reactivity of the metalloligand [Pt₂(µ-S)₂(PPh₃)₄] towards a variety of copper(II)–ligand systems has been studied. Reaction of [Pt₂(µ-S)₂(PPh₃)₄] with copper(II) halide complexes [CuCl₂L](L = 2,2 -bipyridine and 1,10-phenanthroline) gave trinuclear dicationic products [Pt₂(µ-S)₂(PPh₃)₄CuL]²⁺, and the 8-hydroxyquinolinate (hq) complex [Cu(hq)₂] gave [Pt₂(µ-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(µ-S)₂(PPh₃)₄] with CuCl2 and the amine. In contrast, reaction of [Pt₂(µ-S)₂(PPh₃)₄] with CuCl₂ and NH₃ in methanol gave the intensely blue methoxy-bridged dicopper complex [{Pt₂(µ-S)₂(PPh₃)₄Cu(OMe)}₂]²⁺, isolated as its hexafluorophosphate salt. Copper β-diketonate complexes reacted with [Pt₂(µ-S)₂(PPh₃)₄] giving [Pt₂(µ-S)₂(PPh₃)₄Cu(β-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 β-diketonate derivatives show varying stability towards methanolysis, giving [{Pt₂(µ-S)₂(PPh₃)₄Cu(OMe)}₂]²⁺.
Type
Journal Article
Type of thesis
Series
Citation
Devoy, S. M., Henderson, W., Nicholson, B. K., Fawcett, J., & Hor, T. S. A. (2005). Syntheses and ligand interconversions of copper(II) derivatives of the metalloligand [Pt₂(µ-S)₂(PPh₃)₄]. Dalton Transactions, (16), 2780-2787.
Date
2005-07-01
Publisher
Royal Society of Chemistry
Degree
Supervisors
Rights
The final, definitive version of this article has been published in the journal Dalton Transactions (16), (2005), (c) 2005 The Royal Society of Chemistry at the Royal Society of Chemistry webpage.