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

Петров, А. И.; Lutoshkin, Maxim A.

doi:10.1007/s00894-021-04781-6

Cited by 7 publications

(2 citation statements)

References 20 publications

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“…Corresponding data derived from our experiments and from time-dependent density functional theory (TD-DFT) calculations are collected in Table 3. Our TD-DFT protocols match those of other authors that have proven successful for assessing the optical properties of organic dyes and metal complexes [87][88][89]. The electronic spectrum of neutral 2 Ru2Ph-Croc and its change during the first oxidation to the radical cation are depicted in Figure 9.…”

Section: Ir and Uv/vis/nir Spectra Of The Oxidized Forms And Insights From Quantum Chemistrymentioning

confidence: 78%

A “Pretender” Croconate-Bridged Macrocyclic Tetraruthenium Complex: Sizable Redox Potential Splittings despite Electronically Insulated Divinylphenylene Diruthenium Entities

et al. 2021

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Careful optimization of the reaction conditions provided access to the particularly small tetraruthenium macrocycle 2Ru2Ph-Croc, which is composed out of two redox-active divinylphenylene-bridged diruthenium entities {Ru}-1,4-CH=CH-C6H4-CH=CH-{Ru} (Ru2Ph; {Ru} = Ru(CO)Cl(PiPr3)2) and two likewise redox-active and potentially non-innocent croconate linkers. According to single X-ray diffraction analysis, the central cavity of 2Ru2Ph-Croc is shielded by the bulky PiPr3 ligands, which come into close contact. Cyclic voltammetry revealed two pairs of split anodic waves in the weakly ion pairing CH2Cl2/NBu4BArF24 (BArF24 = [B{C6H3(CF3)2-3,5}4]- electrolyte, while the third and fourth waves fall together in CH2Cl2 / NBu4PF6. The various oxidized forms were electrogenerated and scrutinized by IR and UV/Vis/NIR spectroscopy. This allowed us to assign the individual oxidations to the metal-organic Ru2Ph entities within 2Ru2Ph-Croc, while the croconate ligands remain largely uninvolved. The lack of specific NIR bands that could be assigned to intervalence charge transfer (IVCT) in the mono- and trications indicates that these mixed-valent species are strictly charge-localized. 2Ru2Ph-Croc is hence an exemplary case, where stepwise IR band shifts and quite sizable redox splittings between consecutive one-electron oxidations would, on first sight, point to electronic coupling, but are exclusively due to electrostatic and inductive effects. This makes 2Ru2Ph-Croc a true “pretender”.

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Section: Ir and Uv/vis/nir Spectra Of The Oxidized Forms And Insights From Quantum Chemistrymentioning

confidence: 78%

A “Pretender” Croconate-Bridged Macrocyclic Tetraruthenium Complex: Sizable Redox Potential Splittings despite Electronically Insulated Divinylphenylene Diruthenium Entities

et al. 2021

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“…3, a, b). They consist of a pronounced absorption band at 327 nm responsible for overlapping of intraligand n→π* and ligand-tometal charge-transfer (LMCT) transitions (between π-orbitals on I to d-orbitals of platinum, π(I)→d(Pt) [38,39] as well as metal-to-ligand charge-transfer transitions (between d-orbitals of platinum to π-orbitals on S, d(Pt)→π(S)) and dd-electronic transitions with corresponding absorption in the range 370-400 (shoulder-shaped absorption bands) and 442-480 nm.…”

Section: Resultsmentioning

confidence: 99%

Iodide n,π-chelate complexes of platinum(II) based on N-allyl substituted thioureas and their effect on the activity of hepatobiliary system enzymes in comparison with chloride analogs

Orysyk,

Garmanchuk,

Orysyk

et al. 2024

Ukr.Biochem.J.

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The search for new effective drugs in the treatment of neoplasm remains relevant even today, since the adaptation of transformed cells to the action of classical drugs contributes to the emergence of drug resistance. This applies to a number of classic chemotherapy drugs of the platinum series, in particular cisplatin. In this work, we describe the effect of novel analogs of cisplatin on HepG2 cells and on the key enzyme of antioxidant protection system gammaglutamyltranspeptidase, which plays an important role in the acquisition of drug resistance to anticancer drugs by tumor cells. New mononuclear iodide n,π-chelate complexes of Pt(II) with substituted thioureas N-allylmorpholine-4-carbothioamide or 3-allyl-1,1-diethylthiourea were obtained as analogs of cisplatin. All compounds were investigated by UV-Vis, IR, and 1H/13С NMR spectra. Complex I was described by single-crystal X-ray diffraction study. Also, the effect of these analogs on alanine aminotransferase, aspartate aminotransferase, lactate dehydrogenase, which are marker enzymes of liver cells, release of which into the blood indicates liver pathologies, was investigated. All studies were carried out in comparison with chloride n,π-chelate complexes of platinum obtained earlier (however, the effect of these chloride analogs of platinum on enzymes of the hepatobiliary system was investigated for the first time in this work). The results have shown that the studied compounds are better cytostatics/cytotoxics than cisplatin both according to IC50 and apoptosis level of HepG2 cells. It is established that, for the most part, effect of the studied complexes is reduced to a decrease in the degree of malignancy of cells of hepatocyte lines and the activity of LDH and GHT, as well as a decrease in consumed glucose. Keywords: alanine aminotransferase, aspartate aminotransferase, gammaglutamyltranspeptidase, lactate dehydrogenase, NMR spectroscopy, n‚π-chelates, thioureas

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

Петров

Dergachev

2021

Int J of Quantum Chemistry

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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.

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

Cited by 7 publications

References 20 publications

A “Pretender” Croconate-Bridged Macrocyclic Tetraruthenium Complex: Sizable Redox Potential Splittings despite Electronically Insulated Divinylphenylene Diruthenium Entities

A “Pretender” Croconate-Bridged Macrocyclic Tetraruthenium Complex: Sizable Redox Potential Splittings despite Electronically Insulated Divinylphenylene Diruthenium Entities

Iodide n,π-chelate complexes of platinum(II) based on N-allyl substituted thioureas and their effect on the activity of hepatobiliary system enzymes in comparison with chloride analogs

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

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