Abstract
This article deals with complex formation of Bi(III) with 3-mercaptopropanesulfonic acid (H2MPS) in aqueous perchloric acid solutions, with synthesis and characterization of a solid 3-mercaptopropanesulfonate complex of bismuth(III). The stoichiometry and structures of Bi-MPS species in aqueous solution and of a solid complex have been studied by UV–Vis, 1H-NMR, ICP-AES, Raman, and EXAFS spectroscopic methods; the structures have also been simulated with DFT/PBE0 calculations. The Bi(III) LIII-edge EXAFS oscillation for a solid compound with the empirical formula [Bi(HMPS)2(ClO4)]0 was simulated with two Bi–S interatomic distances at 2.50 ± 0.01 Å, two Bi–O distances at 2.56 ± 0.02 Å and two Bi–O distances at 2.75 ± 0.02 Å. Implementation of the same approach for aqueous solutions on the assumption of S3BiO3 coordination at the H2MPS : Bi(III) mole ratio ≥ 3.0 revealed three Bi–S bonds at 2.53 ± 0.02 Å and three Bi–O bonds at 2.68 ± 0.02 Å, respectively. Optimized geometries, electronic structures of Bi(HMPS)3 and [Bi(HMPS)2ClO4]0, vibrational properties of [Bi(HMPS)2ClO4]0, and electronic absorption spectrum of Bi(HMPS)3 species obtained by DFT and TD–DFT modeling are consistent with empirical parameters. In the UV–Vis spectrum of Bi(HMPS)3 the LMCT and MLCT S2− ↔ Bi3+ band appears at 268 nm.
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