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

Abstract

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 BiCl(3) or Bi(NO(3))(3) with mercaptosuccinic, malic, and succinic acids to illustrate the general observation of 1:1 and 1:2 complexes.

The nature of Cu bonding to natural organic matter

“…5f). This coordination fingerprint can be illustrated with thiolactate, a thiolate-carboxylate bifunctional ligand like L-cysteine in proteins (Briand et al, 2004). Similarly to a-OH and a-NH 2 substituted carboxylates, thiolactate is a five-membered heterocycle imposed by the a-SH substitution (Fig.…”

A 3-D bismuth–organic framework containing 1-D cationic inorganic [Bi2O2]2+ chains

“…Low-valent bismuth(II) carboxylate, 1-D polymeric structure, was also prepared using a solid solution of bismuth(0) and bismuth(III) trifluoroacetate in a sealed, evacuated glass ampule heated at 110°C for 2 days [16]. In addition, many other bismuth complexes have been recently synthesized [17][18][19][20][21][22], just to list a few. Bismuth based MOFs, however, are very scarce in the literature [13,23].…”

Crystal structure of 5-bromo-1-hydroxy-2(1H)-pyridinethionedibismuth( III) – dimethylformamid (1:1), Bi2(C5H3BrNOS)6 · C3H7NO

“…The relatively short C-Sd istances (av. 1.720 Å)a so bserved in [Bi(mpo)2Ph] (1.700 Å)and Bi(mpo) 3 (1.707 Å)reveals partial double bond character, and nearly 0.1 Å shorter than the distance (1.81 Å)for asingle bond [9]. The distances (O···S) of average 2.939 Å are similar to that in Bi(mpo)3 (2.934 Å).…”

“…The dihedral angles between planes I/II, II/III, and I/III are 69.57°, 88.80°and 31.67°,respectively. The Bi-S-Cangles of average 102.2°and Bi-O-Na ngles of average 118.2°show that the bonding orbitals of the sulfur atoms are mainly of sp 3 ,and that of oxygen atom are of sp 2 character, similar to H2mp complexes [10]. In the molecular packing N6, O2, O4, O6, O7, S2 and S6 form hydrogen bonds with (1) 2i …”

“…Current interest in bismuth thiolates derives in part from their ability as fungicides, antitumor agents, nanoparticle synthesis and mechanism research of bioactivity [2][3][4][5]. Although Bi(III) compounds of the Bi(mpo) 3 and Bi(ph)(mpo)2 (Hmpo =2 -mercaptopyridine-N-oxide) have been prepared previously [6,7], X-ray structural data are available only for not-substituted base on the pyridine ring. The crystal structure of the title compound is adimer with heptacoordination for each bismuth imposed by three sulfur and four oxygen atoms.…”