Borovyk P. Synthesis, structures and properties of Ru(III), Rh(III), Pd(II), Pt(II) and Ag(I) coordination compounds with N-allyl-substituted carbothioamides.

Українська версія

Thesis for the degree of Candidate of Sciences (CSc)

State registration number

0421U101793

Applicant for

Specialization

  • 02.00.01 - Неорганічна хімія

12-05-2021

Specialized Academic Board

Д 26.218.01

Institute of General and Inorganic Chemistry. VI Vernadsky National Academy of Sciences of Ukraine

Essay

The dissertation is devoted both to the study of Ru(III), Rh(III), Pd(II), Pt(II) and Ag(I) complexation with N-allyl-substituted carbothioamides in solution, and to synthesis, research of molecular structure and physicochemical and medical -biological properties of a number of novel coordination compounds. Optimal synthesis methodics have been developed and 82 novel complex compounds were isolated in the solid state. The structure of 14 complexes was established by the method of single-crystal X-ray diffraction study. The molecular structure was correlated with UV-Vis, IR, 1H NMR, MALDI-TOF mass spectrometry data. For the first time, a number of Cl-, Br- and I-containing n,-chelate complex compounds of Pd(II) and Pt(II) were obtained. In the crystalline state, complexes in the equivalent M: L ratio and bidentate-chelate coordination of the organic ligand by sulfur atoms of the carbotioamide group and (C=C) of the allyl moiety bond were isolated. However, the study of complexation in solution showed that the interaction can take place in the molar ratio M:L=1:1, 1:2, 1:3, which is possible only under the conditions of monodentate coordination of substituted thioamides. The reactions of complexation of Ru3+,2+, Rh3+, Pd2+ and Ag+ ions with heterocycle-containing N-allylthioamides were studied for the first time. A number of novel chelating complexes of molecular, cationic and anionic character, as well as coordination polymer compounds of Ag(I) with realization of polymer chains Ag–S–Ag in their structure have been isolated in the solid state. It was found that the solubility of the obtained compounds depends on the type of complex: ionic compounds are soluble in methanol, partially (or completely) in ethanol and in small concentrations (10-3 – 10-5 mol/l) - in water, while molecular type compounds are soluble only in DMSO and DMF. Polymer complexes of Ag(I) are insoluble in DMSO and DMF. The effect of n,-chelate complexes of Pd(II) and Pt(II) on cells of Allium cepa meristems, Lewis carcinoma and breast microspheroids MCF-7 was studied for the first time. Their effectiveness as potential antiproliferative, cytotoxic and proapoptotic agents has been shown in vitro and in vivo models. The interaction of halide n,-chelate coordination compounds Pd(II), Pt(II) based on 1-allyl-3-(2-hydroxyethyl)thiourea with DNA molecules of plasmid pTZ19R was studied for the first time. Molecular docking has shown that these complexes can interact with DNA by addition through the hydrogen bond between the OH of the ethanolamine group and the guanidine moiety of the DNA. The general mechanism of action of the complexes can be characterized by the formation of single- and double-stranded breaks in DNA plasmid.

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