Identification, Isolation, and Characterization of Cysteinate and Thiolactate Complexes of Bismuth

Although bismuth compounds have been used in medicine for over 200 years, chemical characterization of complexes
involving biological molecules is minimal and mechanisms of bioactivity are ill-defined. The thiophilic nature of
bismuth implicates sulfur centers as likely sites for interaction, and we have exploited this feature to identify,
isolate, and characterize complexes of bismuth with thiolate−carboxylate bifunctional ligands including the amino
acid l-cysteine. The solid-state structures of potassium dichloro(thiopropionato)bismuth (K[1d]), dimethylaminoethanethiolato(thiopropionato)bismuth (4), and dinitrato(cysteinato)bismuthphenanthroline [5(phen)] are compared
with data from electrospray ionization mass spectrometry (ESI-MS). ESI-MS is applied to reactions of BiCl3 or
Bi(NO3)3 with mercaptosuccinic, malic, and succinic acids to illustrate the general observation of 1:1 and 1:2
complexes.