Synthesis and reactivity of gold(III) complexes containing cycloaurated iminophosphorane ligands

Abstract

Transmetallation reactions of ortho-mercurated iminophosphoranes (2-ClHgC₆H₄)Ph₂P NR with [AuCl₄]⁻ gives new cycloaurated iminophosphorane complexes of gold(III) (2-Cl₂AuC₆H₄)Ph₂P NR [R = (R,S)- or (S)-CHMePh, p-C₆H₄F, tBu], characterised by NMR and IR spectroscopies, ESI mass spectrometry and an X-ray structure determination on the chiral derivative R = (S)-CHMePh. The chloride ligands of these complexes can be readily replaced by the chelating ligands thiosalicylate and catecholate; the resulting derivatives show markedly higher anti-tumour activity versus P388 murine leukaemia cells compared to the parent chloride complexes. Reaction of (2-Cl₂AuC₆H₄)Ph₂P NPh with PPh₃ results in displacement of a chloride ligand giving the cationic complex [(2-Cl(PPh₃)AuC₆H₄)Ph₂P NPh]⁺, indicating that the P N donor is strongly bonded to the gold centre.