Comparative (13)C and (31)P NMR studies of the ligand exchange reactions of auranofin with ergothionine, imidazolidine-2-thione and diazinane-2-thione.

ABSTRACT

The interaction of auranofin (Et(3)PAuSATg) with ergothionine (ErS), imidazolidine-2-thione (Imt) and diazinane-2-thione (Diaz) has been studied using (13)C and (31)P NMR spectroscopy. It is observed that these thiones are able to replace both Et(3)P and SATg(-) ligands simultaneously from gold(I) in auranofin forming >C [double bond] S-Au-SATg and [Et(3)P-Au-S [double bond] C<](+) type complexes. The displaced SATg(-) is oxidized to its disulfide (SATg)(2). However, some of the displaced Et(3)P is oxidized to Et(3)PO while the remaining reacts with thiones to form Et(3)P-S [double bond] C< species characterized by delta (31)P NMR of 1.0-1.5 ppm. The Et(3)PO resonance appeared in the 31P NMR spectrum, after 10 days of the addition of ErS, after 19 days of the addition of Imt and after 6 days of the addition of Diaz, to auranofin solution showing that the thiones react with auranofin very slowly.