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TD-DFT assessment of UV-vis spectra palladium and platinum complexes with thiols and disulfides

Authors
  • Petrov, Alexander I.1
  • Lutoshkin, Maxim A.1, 2
  • 1 Federal Research Center “Krasnoyarsk Science Center SB RAS”, Krasnoyarsk, Russian Federation , Krasnoyarsk (Russia)
  • 2 Institut de Recherches sur la Catalyse et l’Environnement de Lyon, Villeurbanne, France , Villeurbanne (France)
Type
Published Article
Journal
Journal of Molecular Modeling
Publisher
Springer-Verlag
Publication Date
May 05, 2021
Volume
27
Issue
6
Identifiers
DOI: 10.1007/s00894-021-04781-6
Source
Springer Nature
Keywords
License
Yellow

Abstract

Time-dependent density functional theory (TD-DFT) and spectrophotometric methods were used for speciation analysis in systems disulfides (cystine, cystamine, homocystine, 3,3-dithiodipropionic acid) — [PdCl4]2− or [PtCl4]2−. We use the M06-2X and CAM-B3LYP density functionals with Def2-SVP basis set to reproduce the experimental UV-vis spectra; the polarized continuum solvation model (PCM) was fitted to take into account solvation effects of the medium (water). Used methods have shown the good agrees with the experiment — theoretical values of transition energies differ from real parameters within ±0.15 eV for functional CAM-B3LYP. Binuclear disulfide complexes of Pd(II) with cystine and cystamine have form S,N-coordination sites, instead of S,S-conformation. It was shown that Pd(II) thiolate complexes formed by cleavage of the disulfide bond exist as [PdCl3L] and [Pd2S2L2]. Pt(II)-disulfide systems have confirmed the presence of [Pt2Cl6(R-SS-R)] and [PtCl4(S-R)] complex species. The DFT/CAM-B3LYP/Def2-SVP/SMD level can be recommended for theoretical estimations of absorption spectra of complexes of palladium or platinum and sulfur-containing ligands.Graphical abstract

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