Affiliations: [a] Department of Chemistry, University of Patras, Patras, Greece
| [b] Department of Chemistry, National and Kapodistrian University of Athens, Athens, Greece
Correspondence:
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Corresponding author. Panayiotis V. Ioannou, Department of Chemistry, University of Patras, 26504 Patras, Greece. Tel.: +30 2610 997 107; Fax: +30 2610 997118; E-mail: [email protected].
Abstract: The reaction of BAL with Sn(IV), SnCl2·2H2O, Pb(II), Ag(I), Cd(II) and Pd(II) gave water-insoluble solids where BAL coordinated using its two sulfur atoms, BAL(S,S)M, while anhydrous SnCl2 gave BAL(O,S)Sn. Apart from the Sn(IV) and Ag(I) which should be monomeric, the structure of the other solids (monomeric or polymeric) could not be established. Indium(III) chloride did not react with either thiophenol or BAL in the absence of a base. In the presence of sodium hydroxide under 1:1:1, 1:2:2 and 1:3:3 molar ratios of InCl3/PhSH/NaOH, the products incorporated the formed sodium chloride and In(SPh)3 was isolated after aqueous work up in the 1:3:3 case. Thallium(III) aceteate gave Tl-SPh and PhSSPh. Thallium(I) acetate and thallium(I) fluoride also gave Tl-SPh in 100% and 75% yields, respectively. The lower yields with TlF is attributed to the non thiophilic HTlF2 formed during the reaction. Theoretical calculations of TlF, (TlF)2 and TlF2- revealed a novel structure of (TlF)2 and shed light to the non thiophilicity of TlF2-. Thallium(I) acetate and BAL gave the expected bis salt while the reactions of TlF under various stoichiometries of BAL:TlF were complicated. Summarizing these and previous results it seems that BAL cannot detoxify heavy metal cations by forming water soluble complexes.
Keywords: British Anti-Lewisite (2,3-dimercapto-1-propanol), complexes with heavy metal cations, thallium fluorides, theoretical calculations
