Complexes of palladium(II) and platinum(II) with mercaptoacetic and 3-mercaptopropionic acids
About: This article is published in Journal of Inorganic and Nuclear Chemistry.The article was published on 1974-05-01. It has received 7 citations till now. The article focuses on the topics: Palladium & Platinum.
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TL;DR: In this article, an ab initio simulation on the thermodynamics of complexation of Bi(III) by 3-mercaptopropionic acid (H2MPA, H2L) was carried out aiming to choose an appropriate quantum chemical methodology.
Abstract: This paper deals with complex formation of Bi(III) with 3-mercaptopropionic acid (H2MPA, H2L) in aqueous perchloric solutions. An extensive investigation on stoichiometry, stability and geometry of complex species in aqueous solutions and of solid H[Bi(MPA)2]·H2O complexes has been carried out by UV-Vis, 1H-NMR, Raman, ICP-AES and EXAFS spectroscopic methods combined with ab initio research. All complex species have cyclic S,O-chelate structures. An ab initio simulation on the thermodynamics of complexation of Bi(III) by H2MPA has been carried out aiming to choose an appropriate quantum chemical methodology. The most accurate results have been achieved with M06 density functional, a SMD solvation model and the Def2-TZVPP basis set with discrepancies of stability constants within ± 1.0 logarithmic units.
9 citations
TL;DR: In this article, the stoichiometry of Pd(II) interactions with dl-homocystine and 3,3′-dithiodipropionic acid were investigated spectrophotometrically in strong hydrochloric acidic media.
Abstract: Stoichiometry of Pd(II) interactions with dl-homocystine and 3,3′-dithiodipropionic acid were investigated spectrophotometrically in strong hydrochloric acidic media. It was established that thiolate and sulfinate complexes are products of a disulfide bond cleavage. It is shown that formation of S,S′-binuclear complexes is necessary for the disproportionation reaction. A multi-spectroscopic (UV-Vis, Raman, NMR, EXAFS) investigation on a disulfide bond state in organic disulfides in complexation processes with Pd(II) was developed. A DFT study on geometry of forming complex species was performed.
6 citations
TL;DR: In this article, the interaction of Pt(II) and Au(III) with disulfides (l-cystine, cystamine, dl-homocystine and 3,3′-dithiodipropionic acid) in hydrochloric acid aqueous solutions was studied.
Abstract: The interaction of Pt(II) and Au(III) with disulfides (l-cystine, cystamine, dl-homocystine and 3,3′-dithiodipropionic acid) in hydrochloric acid aqueous solutions was studied. In the case ...
4 citations
TL;DR: The platinum(II) and palladium (II) complexes [Pt6(SCH2CH2NH2)8]Cl4 and [Pd6[SCH 2CH2OH]8 Cl4· 5H2O with mercamine and β-mercaptoethanol, respectively, were synthesized in this paper.
Abstract: The platinum(II) and palladium(II) complexes [Pt6(SCH2CH2NH2)8]Cl4 and [Pd6(SCH2CH2OH)8 Cl4· 5H2O with mercamine and β-mercaptoethanol, respectively, were synthesized. It was found on the basis of the comparison of IR and X-ray electron spectra of the ligands and complexes, and also of the data of X-ray diffraction analysis that the bidentate coordination of ligands through sulfur and nitrogen atoms is realized in the platinum(II) complex. In the palladium(II) complex β-mercaptoethanol is coordinated in a mixed-mode type. In both complexes sulfur atoms of the ligands occupy a bridging position.
2 citations
TL;DR: When the platinum(II) and palladium (II) salts interact with ligands such as cystamine-(mercamine) HSCH 2CH2NH2 and 2-mercaptoethanol HSCH2CH2OH under certain conditions, polynuclear complexes of the compositions are obtained: [Pt6(SCH2 CH2NH 2)8]Cl4. 5H2O and [Pd6[SCH 2 CH2OH]8]CL4.
Abstract: When the platinum(II) and palladium(II) salts interact with ligands such as cystamine-(mercamine) HSCH2CH2NH2 and 2-mercaptoethanol HSCH2CH2OH under certain conditions, polynuclear complexes of the compositions are obtained: [Pt6(SCH2CH2NH2)8]Cl4. 5H2O and [Pd6(SCH2CH2OH)8]Cl4. In a comparative study of the IR and X-ray spectra of synthesized complexes and ligands, as well as the results of X-ray diffraction studies, it was established that sulfur atoms of 2-mercaptoethanol occupy a bridge position with a mixed coordination of ligands in the palladium complex. In the platinum(II) complex bidentate coordination of ligands is realized through sulfur and nitrogen atoms.
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TL;DR: In this article, a study of the reactivity of five thio-organic compounds with palladiumII ions has been made and one of them, 1-thioglycerol, selected for use as a spectrophotometric reagent for palladium.
16 citations
TL;DR: In this article, the spectrochemical parameters of the involved chromophores are discussed on the assumption of a distorted square-pyramidal structure of the five-coordinated forms.
Abstract: Complexes of NN′-disubstituted thio- or seleno-ureas (L) with bivalent palladium or platinum (Pd, Pt = M) belong mostly to the following types: (i) MIIL4X2(X = halogen), behaving typically as 1 : 1 electrolytes containing the five-co-ordinated cation [MIIL4X]+; (ii)[MIIL4X]ClO4, resulting from replacement of the outer halide ion of MIIL4X2 through ClO4–; (iii) MIIL4(ClO4)2, where one perchlorate tends to be co-ordinated to M, thus again achieving five-co-ordination. True four-co-ordinate species [MIIL2X2] are formed in solution equilibria from [MIIL4X]+ in the presence of an excess of X–, but are not stable in the solid state, except in a few instances with platinum(II). The spectrochemical parameters of the involved chromophores are discussed on the assumption of a distorted square-pyramidal structure of the five-co-ordinated forms; S-bonded thioureas have a position quite close to water in the spectrochemical series of quadratic chromophores, and their optical electronegativity (xopt) is about 2·65, while seleno-ureas have slightly lower values of both the ligand-field strength and xopt.
15 citations