Synthesis and Structures of the First Bismuth−Ester Complexes Using Heterobifunctional Thiolate Anchored Ligands and Mass Spectrometric Identification of Ligand-Bridged Derivatives

Abstract

The first systematic series of bismuth complexes involving ester donors, Bi(SCH(2)C(O)OCH(2)CH(3))Cl(2), Bi(SCH(2)C(O)OCH(3))(2)Cl, and Bi(SCH(2)COOCH(3))(3), has been isolated and characterized by spectroscopic (IR, Raman) and X-ray crystallographic data. In addition, these and other species have been identified by electron-impact, electrospray, and atmospheric pressure chemical ionization mass spectometry. The generally applicable synthetic methodology involves the use of heterobifunctional ligands containing a thiolate moiety as an anchor to facilitate coordinate interactions between weak donors (carbonyls) and weak acids (bismuth). The bifunctional nature of the ligands is manifested in both chelating and bridging roles. Important comparisons can be made with the pharmaceutical agent "colloidal bismuth subcitrate" (CBS). The observations allow for a new appreciation of bioactive bismuth compounds, by providing an approach to study the interaction of biorelevant functional groups with bismuth.

Identification of complexes containing glutathione with As(III), Sb(III), Cd(II), Hg(II), Tl(I), Pb(II) or Bi(III) by electrospray ionization mass spectrometry

“…The high energies typically employed in electron ionization (EI) and chemical ionization (CI) mass spectrometric techniques are avoided in ESI-MS, facilitating the observation of m/z values corresponding to molecular ions with minimum or no fragmentation. The technique is suited to solutions containing preformed ions, making it appropriate for inorganic compounds, including systems containing complexes of metals and metalloids [24,25,[27][28][29][30][31][32][33][34]. We have recently used electrospray ionization mass spectrometry [35] (ESI-MS) to identify complexes for naturally occurring amino acids with each of the toxic heavy metals, cadmium, mercury, thallium and lead, and the less-toxic and medicinally relevant [36,37] heavy metal, bismuth.…”

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].…”

Dinuclear platinum complexes with designer thiolate ligands from the monoalkylation of [Pt2(μ-S)2(PPh3)4]

“…Some of these complexes were previously identified in our earlier screening study [5]. Although metal complexes of the thiolate ligands PhNHC(O)CH 2 S À [15,16] and MeO 2 CCH 2 S À [17][18][19] are well known, and the thiols PhC(O)CH 2 SH [20] and EtO 2 CCH 2 C(O)CH 2 SH [21] are reported, the other thiolate ligands (or the free thiols) contained in complexes 3e-3o appear to be new ligands.…”