Reactions of dl-homocystine and 3,3′-dithiodipropionic acid with Pd(II) in aqueous hydrochloric solutions. Part I: coordination model

Journal of Coordination Chemistry

Novikova

Demina

et al. 2019

Self Cite

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 of Pt(II), the oxidative addition reaction leads to the formation of the Pt(IV) thiol complex. In the case of Au(III) disulfide binding causes a reduction to Au(0) and oxidation of the disulfide to sulfonic acid. Cyclic voltammetry and different spectroscopic methods were used to study the process. The pattern of influence of the metallic properties for d 8 ions in the direction of the reaction was found.

Section: {Table 4}supporting

confidence: 72%

Section: {Table 3} {Figure 4}mentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

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Interaction of Pt(II) and Au(III) with organic disulfides in hydrochloric aqueous solution

Journal of Coordination Chemistry

Novikova

Demina

et al. 2019

Self Cite

“…Spectrophotometric titrations, performed earlier, indicate substantially different interconversion products, given the original structural similarity of all four disulfides. − We believe this effect is specifically due to the presence of Pd 2+ metal ion, which mediates different RSSR/RSH interconversion mechanisms for different disulfides. Indeed, both l -cystine and cystamine form stable S,N′-binuclear and S,S′,N,N′-tetranuclear complexes without cleavage of the disulfide bond. , In opposite, in the interconversion of dl -homocystine and 3,3′-dithiodipropionic acid, which are homologues of l -cystine, the S–S bond undergoes disproportionation under the same conditions.…”

Section: Introductionmentioning

confidence: 86%

Palladium(II) Ion Mediated Disulfide/Thiolate Interconversion: Predicting the Disulfide Group State from First Principles

Dergachev

2019

J. Phys. Chem. A

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Different reactivity of homologous disulfides toward Pd2+ was previously reported: stepwise complexation to Pd2+ for l-cystine and cystamine ligands, while for dl-homocystine and 3,3′-dithiodipropionic acid, disulfide’s disproportionation toward thiolate and sulfinic acid complexes is observed. The disulfide/thiolate interconversion of four different disulfide ligands in the presence of nonredox metal cation Pd2+ in aqueous solution has been computationally investigated. We see this different reactivity in different capacities of considered homologous disulfides to stabilize forming S,S′-binuclear complexes, which are believed to be key intermediates toward interconversion products. We thus devise a theoretical model that rationalizes experimentally observed phenomenon of disulfides different reactivity toward nonredox transition metal cation Pd2+.

“…DFT calculations predicted that the formation of S,S 0 -binuclear complexes is a critical intermediate step for determining reaction pathways. The products of these reactions in aqueous solutions are thiolate and sulfinic acid complexes of Pd(II) [17][18][19][20].…”

Section: Introductionmentioning

confidence: 99%

Platinum(II)‐mediated disulfide/thiolate interconversion in organic disulfides: Density functional theory thermodynamic study

Int J of Quantum Chemistry

Dergachev

2021

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We present a complete Density Functional Theory (DFT) study of the thermodynamics of the reactions of disulfides (L-cystine, cystamine, DL-homocystine, and 3,3 0dithiodipropionic acid) with Pt(II) ions in aqueous media. SMD solvation model was fitted to take into account the solvation effects of the medium. DFT calculations predict the oxidative addition reaction with the formation of thiolate complexes of Pt(IV)-[PtCl 4 (S-R) 2 ] which is consistent with experimental data. We propose a theoretical model that rationalizes the experimental data on Pt(II) interactions with homological disulfides. The role of explicit solvation in reactions is also investigated. We propose that the stability of S,S 0 -binuclear disulfide complexes correlates with the redistribution of charges on sulfur atoms. We compared MN15 and PBE0 functionals for the calculation of equilibrium constants.