Abstract
Electrospray ionization spectra of potential cyanide-containing gold-drug metabolites revealed additional, weak, unanticipated peaks at approximately twice the mass of the gold(I) and gold(III) cyanide complexes. The exact masses correspond to proton-linked bimetallic complexes, [H{Au(CN) m } 2] −, ( m = 2,4). Further investigation revealed a total of 12 examples, including trimetallic complexes, [H 2{Au(CN) m } 3] −; mixed species with two complexes, [H{Au(CN) 2}{Au(CN) 4}] −; and thiolato species, [H{(RS)Au(CN) 3} 2] −. trans-[AuX 2(CN) 2Cl 2] − and trans-[AuX 2(CN) 2Br 2] − generated 35Cl/ 37Cl and 79Br/ 81Br isotopic patterns for the protonated bi- and tri-metallic analogues which were in good agreement with the presence of four or six halide ligands, respectively. Concentration-dependent studies demonstrated that the signals are independent of the solution concentrations of mono-metallic precursors, suggesting formation in the gas phase during or following droplet desolvation.
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