iodine/proton cyclization, N-allylcarbothioamides, Ru(ІІ,III), Rh(III) and Pd(II) complexes, chelated metalocycles, UV-Vis spectra, 1H NMR.

How to Cite

Borovyk, P., Litvinchuk, M., Bentya, A., Orysyk, S., Zborovskii, Y., Orysyk, V., Pekhnyo, V., & Mykhailo, V. (2020). SYNTHESIS AND SPECTRAL CHARACTERISTICS OF THE Ru(III,ІІ), Rh(III) AND Pd(II) COMPLEXES BASED ON N-ALLYLTHIOAMIDES AND PRODUCTS THEIR PROTON- AND IODOCYCLIZATION . Ukrainian Chemistry Journal, 86(4), 63-90.


The paper shows the possibility of using N-allylthioamides H2L1-H2L3 and products of their proton / iodine cyclization HL4, HL5 as chelating agents in the complexation reactions with Ru(III,II), Rh(III) and Pd(II) ions. As a result, a series of new chelating complexes of [M(HL1-3)Cl2(H2O)2], [M(HL1-3)2(H2O)2]Cl (2), [М(HL1-3)2(H2O)Cl] (3), [Ru(HL1-3)(PPh3)2]Cl (4), K[Pd(HL1-3)Cl2] (5), [Pd(HL1-3)2] (6), [M(L4,5)2(H2O)2]Cl (7), K[Pd(L4,5)Cl2] (8), [Pd(L4,5)2] (9) in which the ligands are coordinated to the metal ions by O,S- or O,N-bidentate chelate manner in a monodeprotonated form, where synthesis, isolated in solid state and characterized by the methods of elemental chemical analysis, 1H NMR, IR and UV-Vis spectroscopy. It was found that HL4,5, when complexed, is converted to the corresponding tautomeric form with O,N-coordination through the oxygen atoms of the deprotonated hydroxyl group and the nitrogen atoms of the dihydrothiazolyl ring. It has been established that the allyl moiety does not participate in the formation of a coordination bond with the Ru (III,II), Rh(III) and Pd(II) ions, which is probably due to the presence in the molecules of ligands of other donor nucleophilic centers located in advantageous position for the formation of six-membered chelated metal cycles. In contrast to complexes 1-9, the compounds of [M(HL6)2(H2O)2Cl2]Cl (10), [Pd(HL6)2Cl2] (11) based on 2-(5-(iodomethyl)-1,3-thiazolidin-2-ylidene) malononitrile (HL6) were obtained with monodentate coordination of the ligand in molecular form, which is caused by the presence of two nitrile groups in the HL6 molecule with sp-hybridization of the nitrogen atomic orbitals, which provides almost linear overlap with the d-orbitals of the metal atom upon formation of CN→M bond. The study of the complex formation of metal chlorides with H2L1-H2L3 by the method of isomolar series and UV-Vis spectra showed that there is interaction in the M: L = 1:1, 1:2, 1:3 molar ratio (in the case of Ru3+, Rh3+ ions) and 1:1, 1:2 (in the case of Pd2+ and Ru2+ ions) which is related to the coordination capacity of metals and their ability to form octahedral (for Ru3+, Rh3+ ions) or square-planar (for Pd2+ ions) coordination unit. The reaction of Ru3+, Rh3+ and Pd2+ ions with HL4, HL5 in the isopropanol solution also occurs in the ratio M:L = 1:1, 1:2, 1:3, however, the titration curves are much less pronounced compared to complexes based on H2L1-H2L3. In the interaction of HL6 with the ions of the above metals, the curve has the appearance of an almost straight line, indicating the so-called "state of unsaturation" of the system in the corresponding concentration range due to the monodentate coordination of HL6. The solubility study of the obtained complexes showed that ionic type compounds 2, 4, 5, 7, 8, 10 were dissolved in methanol, partially (or completely) in ethanol, and at low concentrations (10-3-10-5 mol/l) - in water, while molecular type compounds 1, 3, 6, 11 are soluble in DMSO and DMF only.


1. Okamoto K., Kuwabara J., Kanbara T. Secondary thioamides as multidentate ligands for functional metal complexes. Chemistry Letters. 2015. 44(2): 102.
2. Begum R.A., Powell D., Bowman-James K. Thioamide pincer ligands with charge versatility. Inorganic Chemistry. 2006. 45, N 3: 964.
3. Kanchanadevi A., Ramesh R., Semeril D. Efficient and recyclable Ru(II) arene thioamide catalysts for transfer hydrogenation of ketones: Influence of substituent on catalytic outcome. Journal of Organometalic Chemistry. 2016. 808: 68.
4. Ahlford K., Ekström J., Zaitsev A.B., Ryberg P., Eriksson L., Adolfsson H. Asymmetric transfer hydrogenation of ke-tones catalyzed by amino acid derived rho-dium complexes: On the origin of enantioselectivity and enantioswitchability. Euopian Journal of Chemistry. 2009. 15, N 42: 11197.
5. Liu J., Wang H., Zhang H., Wu X., Zhang H., Deng Y., Yang Z., Lei A. Identification of a highly efficient alkylated pincer thioimido–palladium(II) complex as the active catalyst in Negishi coupling. Euopian Journal of Chemistry. 2009. 15, N 17: 4437.
6. Kuwabara J.; Kanbara T. Synthesis and optical properties of pincer palladium and plat-inum complexes having thioamide units. Journal of Photopolymer Science Technolo-gy. 2008. 21, N 3: 349.
7. Yamada M., Gandhi M.R., Shibayama A. Rapid and selective recovery of palladium from platinum group metals and base metals using a thioamide-modified calix[4]arene extractant in environmentally friendly hy-drocarbon fluids. Scientific Reports. 2018. 8, N 1: 16909.
8. Yamada M., Gandhi M.R., Sato D., Kaneta Y., Kimura N. Comparative study on palla-dium(II) extraction using thiamide-modified acyclic and cyclic extractants. Industrial & Engineering Chemistry Research. 2016. 55, N 33: 8914.
9. Hess S.M., Anderson J.G., Bierbach U. A non-crosslinking platinum–acridine hybrid agent shows enhanced cytotoxicity com-pared to clinical BCNU and cisplatin in glioblastoma cells. Bioorganic & Medicinal Chemical Letters. 2005. 15: 443.
10. Zhou Q., You C., Ling Y., Wu H., Sun B. pH and thermo dual stimulus-responsive liposome nanoparticles for targeted delivery of platinum-acridine hybrid agent. Life Sci-ence. 2018. 217: 41-48 doi: 10.1016/j.lfs.2018.11.052.
11. Repich H.H., Orysyk V.V., Palchykovska L.G., Orysyk S.I., Zborovskii Yu.L., Vasylchenko O.V., Storozhuk O.V., Biluk A.A., Nikulina V.V., Garmanchuk L.V., Pekhnyo V.I., Vovk M.V. Synthesis, spectral characterization of novel Pd(II), Pt(II) π-coordination compounds based on N-allylthioureas. Cytotoxic properties and DNA binding ability. Journal of Inorganic Biochemistry. 2017. 168: 98.
12. Correa R.S., de Oliveira K.M., Delolo F.G., Alvarez A., Mocelo R., Plutin A.M., Cominetti M.R., Castellano E.E., Batista A.A. Ru(II)-based complexes with N-(acyl)-N′,N′-(disubstituted)thiourea ligands: Syn-thesis, characterization, BSA- and DNA-binding studies of new cytotoxic agents against lung and prostate tumour cells. Journal of Inorganic Biochemistry. 2015. 150: 63.
13. Cunha B.N., Colina-Vegas L., Plutin A.M., Silveira R.G., Honorato J., de Oliveira K.M., Cominetti M.R., Ferreira A.G., Castellano E.E., Batista A.A. Hydrolysis reaction promotes changes in coordination mode of Ru(II)/acylthiourea organome-tallic complexes with cytotoxicity against human lung tumor cell lines. Journal of In-organic Biochemistry. 2018. 186: 147.
14. Adhikari S., Hussain O., Phillips R.M., Kaminsky W., Kollipara M.R. Neutral and cationic half-sandwich arene d6 metal com-plexes containing pyridyl and pyrimidyl thiourea ligands with interesting bonding modes: Synthesis,structural and anti-cancer studies. Applied Organometallic Chemistry. 2018. e4476, 10.1002/aoc.4476.
15. Zhao Y., Wang L., Guo C., Jiang B., Li X., Liu K., Shi D. Metal complexes of thiosemicarbazones as potent anticancer agents: a minireview. Journal of Clinical Medicinal Research. 2018. 2, N 2:180009; doi: 10.21127/yaoyimr20180009.
16. Zhang B., Luo H., Xu Q., Lin L., Zhang B. Antitumor activity of a transthiosemicarbazone schiff base palladium (II) complex on human gastric adenocarcinoma cells. Oncotarget. 2017. 8, N 8:13620.
17. Tavares T.T., Paschoal D., Motta E.V.S., Carpanez A.G., Lopes M.T.P., Fontes E.S., Dos Santos H.F., Silva H., Grazul R.M., Fontes A.P.S. Platinum(II) and palladium(II) arylthiosemicarbazone complexes: synthesis, characterization, molecular mod-eling, cytotoxicity, and antimicrobial activity. Journal of Coordination Chemistry. 2014. 67, N 6: 956.
18. Würthner F., Schmidt J., Stolte J., Wortmann R. Hydrogen-Bond-Directed Head-to-Tail Orientation of Dipolar Merocyanine Dyes: A Strategy for the Design of Electrooptical Materials. Angewandte Chemie International Edition. 2006. 45(23): 3842.
19. Krasnaya Zh.A., Kachala V.V., Zlotin S.G. Synthesis and conformations of cross-conjugated polyenes containing heterocyclic moieties with diverse structures. Mendeleev Communication. 2014. 24(23): 377.
20. Orysyk S.I., Borovyk P.V., Repich H.H., Severynovska O.V., Zborovskii Yu.L., Mishchenko A.M., Orysyk V.V., Pekhnyo V.I., Vovk M.V. Synthesis, spectral characterization and DFT calculations of novel Ag(I) π-coordination polymeric complexes based on N- allylmorpholine-4-carbothioamide. Journal of Molecular Structure. 2020. 1208: 127866.
21. Borovyk P.V., Litvinchuk M.B., Bentya A.V., Orysyk S.I., Zborovskii Yu.L., Slyvka N.Yu, Orysyk V.V, Pekhnyo V.I., VoVk M.V. Zn(II) and Ag(I) complexes of N-allythioamides of pyrimidinyl (cyclohexenyl) carboxylic acids and prod-ucts their proton- and iodocyclization. Ukr. Chim. Zhurn. 2019. 85(3): 3.
22. Liver E. Electronic Spectroscopy of Inorganic Compounds. Part 1. Moscow, «Mir» 1987, P. 393, 298, 259.
23. Liver E. Electronic Spectroscopy of Inorganic Compounds. Part 2. Moscow, «Mir» 1987, P. 99-109.
24. Klimova V.A. The main micro methods of analysis of organic compounds. – Moscow: Chemistry, 1967.- P.19-55, 101-107.
25. WesoIowska A., Jagodziñski T.S., Sosnicki J.G., Hansen P.E. Synthesis of the N-Allylthioamide Derivatives of Cyclic Oxo- and Dioxo- Acids and Their Cyclization to the Derivatives of 4,5-Dihydrothiazole. Polish Journal Chemistry. 2001. 75: 387.
26. Hansen P.E., Duus F., Bolvig S., Jagodzinski T.S. Intramolecular hydrogen bonding of the enol forms of β-ketoamides and β-ketothioamides. Deuterium isotope effects on 13C chemical shifts. Journal of Molecular Structure. 1996. 378: 45.
27. Litvinchuk M.B., Bentya A.V., Slyvka N.Yu, Vovk M.V. 5-Functionalized (1,3-thiazolidin-2-ylidene) pyrimidine-2,4,6-trione. Ukr. Chim. Zhurn. 2017. 83(10): 90.
28. Kazitsyna L.A. The use of UV, IR and NMR spectroscopy in organic chemistry / Kazitsyna L.A., Kupletskaya N.B. - Moscow: Higher School, 1971. 265 .
29. Litvinchuk M.B., Bentya A.V., Slyvka N.Yu, Vovk M.V. Halogen cyclization of the products of the addition of allyl isothiocyanate to acyclic methylene active compounds. Russian Journal of Organic Chemistry. 2017. 53(5): 699.


Download data is not yet available.