The influence of competitive coordination, a tautomeric form of functionally substituted thioamides, conditions of synthesis and nature of the metal on the course of the reaction and structure of mono-, bi, and polynuclear complexes of 3d, 4d-metals is considered based on results obtained in the Department of "Chemistry of Complex Compounds" of the V.I. Vernadsky Institute of General and Inorganic Chemistry NAS of Ukraine, together with the staff of the Department of “Chemistry of Heterocyclic Compounds” of the Institute of Organic Chemistry NAS of Ukraine.
The influence of ligand denticity, as well as conditions of complex formation on the structure of obtained complexes and their polymorphic modifications, was studied based on the reaction of d-metals with functionally substituted N, S- and O, N, S-containing thioamides. In addition, it is proved the influence of tautomeric forms of thioamides on the stereochemistry of coordination polyhedra: it is found that the thionic tautomeric form promotes the transposition of thioureas, while the thiol form promotes its cis-position in the square-planar of a polyhedron of 3d, 4d-metals in the structure of complexes. However, it was found that the thion tautomeric form leads to the formation of octahedral, while the thiol form to the square-planar of coordination nodes in complexes of Cu(II) and Ni(II), which are characterized by a change in coordination polyhedra (from square-planar and tetrahedron to octahedron) that depending on the strength of the ligand field. It is obvious that this effect of tautomeric forms of thioamides is associated with the formation of a conjugate system of double bonds in their molecules. In this case, the transition of thioamide to thiol form depends on the pH and the nature of the organic solvent: in a weakly alkaline medium or polar organic solvent (pyridine, chloroform) there is a shift of equilibrium towards to the dominance of thiol tautomeric form.
It was found that the thionic tautomeric form of thioamides (depending on pH and substituent composition) reacts with metal salts mainly in neutral form or in the monoanionic form, forming complexes of molecular or ionic nature, while thiol form reacts in the form of dianion, forming complexes preferably anionic type. Ionic compounds are usually soluble or sparingly soluble in water in low concentrations (10-3–10-5 mol/l), while compounds of the molecular type are soluble only in DMSO and DMF.
It is shown that the stereoselective synthesis of various ligand complexes is carried out mainly in three ways: 1) by the interaction of the initial components in the corresponding stoichiometry. In this case, the vacancy in the metal environment is occupied by either the anions of the starting metal salt (Hal-, SO42-, NO3-, CH3COO-, etc.) or other organic molecules (triphenylphosphine, pyridine, etc.); 2) carrying out parallel reactions (hydrolysis and oxidation of thioureas), which lead to participation in the coordination of by-products of the reaction; 3) carrying out reactions with intraligand rearrangements, which leads to the cyclization of organic ligands and coordination of the products of their transformation to the central metal ion. However, it was found that hydrolysis / oxidation or intraligand cyclization of substituted polydentate thioamides can occur both under the action of synthesis conditions and under the action of complexing metals as promoters of organic reactions.
It was found that depending on the temperature and time of interaction of the starting reagents, different polymorphic modifications of complexes (triclinic or monoclinic) are formed, which differ in packing density and the nature of intermolecular interactions. As a result, such polymorphic modifications have different solubilities in water, which is important for the controlled synthesis of appropriate structures and their practical application.
Garnovskii A.D., Garnovskii D.A., Vasil'chenko I.S., Burlov A.S., Sadimenko A.P., Sadekov I.D. Competing coordination: ambident ligands in the modern chemistry of metal complexes. Russ Chem. Rev. 1997. 66 (5): 389–416. (In Russian). doi: 10.1070/RC1997v066n05ABEH000258.
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. Angew. Chem. Int. Ed. 2006. 45 (23): 3842–3846.
Krasnaya Zh.A., Kachala V.V., Zlotin S.G. Synthesis and conformations of cross-conjugated polyenes containing heterocyclic moieties with diverse structures. Mendeleev Commun. 2014. 24 (6): 377–379.
Okamoto K., Kuwabara J., Kanbara T. Secondary thioamides as multidentate ligands for functional metal complexes. Chem. Lett. 2015. 44 (2): 102–110.
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. J. Organomet. Chem. 2016. 808: P. 68–77.
Ahlford K., Ekström J., Zaitsev A.B., Ryberg P., Eriksson L., Adolfsson H. Asymmetric transfer hydrogenation of ketones catalyzed by amino acid derived rhodium complexes: On the origin of enantioselectivity and enantioswitchability. Chem. Eur. J. 2009. 15 (42): 11197–11209.
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. Chem. Eur. J. 2009. 15 (17): 4437–4445.
Paul P., Datta S., Halder S., Acharyya R., Basuli F., Butcher R.J., Peng S.-M., Lee G.-H., Castineiras A., Drew M.G.B., Bhattacharya S. Syntheses, structures and efficient catalysis for C–C coupling of some benzaldehyde thiosemicarbazone complexes of palladium. J. mol. catal. a: 2011. 344 (1): 62–73.
Hakimi M., Vahedi H., Takjoo R., Rezaeifard A. Nanoporous silica supported novel copper(II) thiosemicarbazone complexes as selective and reusable catalysts for oxidation of alcohols using H2O2. Int. J. ChemTech Res. 2012. 4 (4): 1658–1665.
Manikandan R., Anitha P., Prakash G., Vijayan P., Viswanathamurthi P., Butcher R.J., Malecki J.G. J. Ruthenium(II) carbonyl complexes containing pyridoxal-thiosemicarbazone and trans-bis(triphenylphosphine/arsine): Synthesis, structure and their recyclable catalysis of nitriles to amidesand synthesis of imidazolines. J. mol. catal. a: 2015. 398: 312–324.
Anitha P., Viswanathamurthi P., Kesavan D., Butcher R.J.J. Ruthenium(II) 9,10-phenanthrenequinone thiosemicarbazone complexes: synthesis, characterization, and catalytic activity towards the reduction as well as condensation of nitriles. J. Coord. Chem. 2015. 68 (2): 321–334.
Kuwabara J.; Kanbara T. Synthesis and optical properties of pincer palladium and platinum complexes having thioamide units. J. Photopolym. Sci. Technol. 2008. 21 (3): 349–353.
Hernández W., Paz J., Carrasco F., Vaisberg A., Spodine E., Manzur J., Hennig L., Sieler J., Blaurock S., Beyer L. Synthesis and characterization of new palladium(II) thiosemicarbazone complexes and their cytotoxic activity against various hu-man tumor cell lines. Bioinorg. Chem. Appl. 2013. 5: 1456–1462.
Hitesh D., Patel H.D., Shah Der S.A. Synthesis and anti-cancer activity of new thiosemicarbazones of 1-(5-chloro-1H-benzimidazol-2-yl) ethanone. Der Pharm. Sinica. 2012. 3 (2): 199–210.
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. 2019. 217: 41–48.
Khan M.R., Zaib S., Khan A., Badshah A., Rauf M.K., Imtiazud-Din, Tahir M.N., Shahid M., Iqbal J. Pd(II)-based heteroleptic complexes with N-(acyl)-N′,N′-(disubstituted)thioureas and phosphine li-gands: Synthesis, characterization and cyto-toxic studies against lung squamous, breast adenocarcinoma and Leishmania tropica. Inorg. Chim. Acta. 2018. 479: 189–196.
Patel A.L., Chaudhary M.J. Synthesis, characterization and antimicrobial studies on bivalent copper, nickel and cobalt complexes of thiosemicarbazone. Int. J. ChemTech Res. 2012. 4 (3): 918–924.
Ahmad S., Nadeem S., Anwar A., Hameed A., Tirmizi S.A., Zierkiewicz W., Abbas A., Isab A.A., Alotaibi M.A. Synthesis, characterization, DFT calculations and antibacterial activity of palladium(II) cyanide complexes with thioamides. J. Mol. Struct. 2017. 1141: 204–212.
Aziz N.M., Abdullah B.H. Synthesis, cytotoxicity, antibacterial activity and molecular modeling study of new mono, homo and heterobimetallic complexes of palladium(II) with some transition metal ions containing the ligands N-phenyl-N’-(2-thiazolyl)thiourea and diphosphines Ph2P(CH2)n PPh2 (Where n = 1-3). Indian J. Chem. Sec. A. July 2019. 58: 772–782.
Haas K.L., Franz. K.J. Application of metal coordination chemistry to explore and manipulate cell biology. Chem. Rev. 2009. 109 (10): 4921−4960.
Chen J., Fukuzumi K., Ip B., Flo-rence Cid A.P. Metal Coordination chemistry in the study of biological pathway and processes: A review. Int. J. Pharm. Biol. Chem. Sci. 2014. 3 (3): 36−45.
Dilworth J.R., Hueting R. Metal complexes of thiosemicarbazones for imaging and therapy. Inorg. Chim. Acta. 2012; 389: 3−15.
Pelosi G. Thiosemicarbazone metal complexes: From structure to activity. Open Crystall. J. 2010. 3 (2): 16−28.
Hossain Md.S., Roy P.K., Ali R., Zakaria C.M., Kudrat-E-Zahan Md. Selected pharmacological applications of 1st row transition metal complexes: A review. Clinical Med. Res. 2017. 6 (6): 177−191.
Zhao Y., Wang L., Guo C., Jiang B., Li X., Liu K., Shi D. Metal complexes of thiosemicarbazones as potent anticancer agents: a minireview. Med. Res. 2018. 2 (2): 180009. doi: 10.21127/yaoyimr20180009.
Hossain Md.S., Zakaria C.M., Kudrat E-Zahan Md. Metal complexes as potential antimicrobial agent: A review. American J. Heterocycl. Chem. 2018. 4 (1): 1–21.
Patra M. Gasser G. Organometallic compounds: An opportunity for chemical biology? ChemBioChem. 2012. 13 (9): 1232–1252.
Barnard C. Platinum Group Metal Compounds in Cancer Chemotherapy. Johnson Matthey Technol. Rev. 2017. 61 (1): 52–59.
Medici S., Peana M.F., Zoroddu M.A. Noble Metals in Pharmaceuticals: Applications and Limitations. Biomed. Appl. Met. 2018. 3–48. doi: 10.1007/978-3-319-74814-6_1
Stevens S.K., Strehle A.P., Miller R.L., Gammons S.H., Hoffman K.J., McCarty J.T., Miller M.E., Stultz L.K, Hanson P.K. The anticancer ruthenium complex KP1019
induces DNA damage, leading to cell cycle delay and cell death in Saccharomyces cerevisiae. Mol. Pharm. 2012. 83 (1): 225–234.
Welsh A., Rylands L., Arion V., Prince S., Smith G. Synthesis and antiproli-ferative activity of benzimidazole-based, trinuclear neutral cyclometallated and cationic, N^N-chelated ruthenium(II) complexes. Dalton Trans. 2020. (4): doi: 10.1039/c9dt03902c.
Alessio E. Thirty Years of the Drug Candidate NAMIA and the Myths in the Field of Ruthenium Anticancer Compounds: A Personal Perspective. Eur. J. In-org. Chem. 2017. (12): 1549–1560.
Florindo P.R., Pereira D.M., Borralho P.M., Rodrigues C.M.P., Piedade M.F.M., Fernandes A.C. Cyclopentadienyl–ruthenium(II) and iron(II) organometallic compounds with carbohydrate derivative ligands as good colorectal anticancer agents. J. Med. Chem. 2015. 58 (10): 4339–4347.
Zhang B., Luo H., Xu Q., Lin L., Zhang B. Antitumor activity of a trans-thiosemicarbazone schiff base palladium(II) complex on human gastric adenocarcinoma cells. Oncotarget. 2017. 8 (8): 13620–13631.
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 com-plexes: synthesis, characterization, molecular modeling, cytotoxicity, and antimicrobial activity. J. Coord. Chem. 2014. 67 (6): 956–968.
Orysyk S.I., Bon V.V., Zholob O.O., Pekhnyo V.I., Orysyk V.V., Zborovs-kii Yu.L., Vovk M.V. Novel Pd(II) coordination compounds involving 2-[(2-Hydroxyphenyl)methylene]hydrazine-N-(2-propenyl)-carbothioamide as a ligand or proligand: Synthesis, crystal structures and analytical application. Polyhedron. 2013. 51: 211–221.
Orysyk S.I., Repich G.G., Bon V.V., Dyakonenko V.V., Orysyk V.V., Zbo-rovskii Yu.L., Shishkin O.V., Pekhnyo V.I., Vovk M.V. Novel Fe(III), Co(III), Ni(II), Cu(II) coordination compounds involving 2-[(2-hydroxyphenyl)methylene]hydrazine-N-(2-propenyl)-carbothioamide as ligand: Synthesis, crystal structures and spectral characteristics. Inorg. Chim. Acta. 2014. 423: 496–503.
Repich H.H., Orysyk S.I., Severynovska O.V., Pekhnyo V.I. Correlation of spectral methods of analysis and X-ray dif-fraction in determining the different types of coordination of thiosemicarbazone in the Ni(II) complex. Ukr. Chem. J. 2015; 81 (3): 8-15. (In Ukrainian).
Orysyk S.I., Bon V.V., Obolentseva O.V., Zborovski Yu.L.i, Orysyk V.V., Pekhnyo V.I., Staninets V.I., Vovk V.M. Synthesis, structural and spectral characteri-zation of Zn(II) complexes, derived from thiourea and thiosemicarbazide. Inorg. Chim. Acta. 2012. 382: 127–138.
Gudasi K.B., Patil S.A., Bakale R.P., Nethaji M. Ligational behaviour of (E)-2-amino-N′-[1-(2-hydroxyphenyl) ethylidene]-benzohydrazide towards later 3d metal ions: X-ray crystal structure of nickel(IV) complex. J. Mol. Struct. 2014. 1065-1066: 179–185.
Shawish H.B., Paydar M., Looi C.Y., Wong Y.L., Movahed E., Halim S.N.A., Wong W.F., Mustafa M-R., Maah M.J. Nickel(II) complexes of polyhydrox-ybenzaldehyde N4-thiosemicarbazones: synthesis, structural characterization and antimicrobial activities Trans. Met. Chem. 2014. 39: 81–94.
Nefedov V.I. X-ray electronic spectroscopy of chemical compounds. Moscow: Chemistry. 1984. p. 256. (In Russian).
Orysyk S.I. Investigation of the structure of Ru(III), Rh(III) and Pd(II) coordination compounds with ambient O,N,S-containing lignans by X-ray photoelectron spectroscopy. Ukr. Chem. J. 2008. 72 (10): 65-77. (In Ukrainian)
Bon V.V., Orysyk S.I., Pekhnyо V.I., Volkov S.V. Square-planar 1:2 Ni(II) and Pd(II) complexes with different coordination mode of salicylaldehyde (4)-phenylthiosemicarbazone: Synthesis, structure and spectral properties. J. Mol. Struct. 2010. 984: 15-22.
Bon V.V., Orysyk S.I. Pekhnyo V.I. [1-(2-Oxidobenzylidene)-4-phenylthiosemicarbazidato-κ3O,N1,S](pyridine-κN)-copper(II). Acta Cryst. E. 2010; 66 (6): m676–m676.
Orysyk S.I. Coordination chemistry of series 3d, 4d-metals with ambident functional substituted hydrazides, imines and carbothioamides: dis. ... Dr. of Science in Chemistry, specialty 02.00.01 – inorganic chemistry. V.I. Vernadsky Institute of General and Inorganic Chemistry of the National Academy of Sciences of Ukraine, Kyiv, 2017. p. 446.
Bon V.V., Orysyk S.I., Pekhnyo V.I., Orysyk V.V. and Volkov S.V. Synthe-sis and spectroscopic investigations of Rh(III) and Pd(II) complex compounds with N-(pyridine-2-yl)-morpholine-4-carbothioamide. Polyhedron. 2007. 26 (13): 2935-2941.
Bon V.V., Orysyk S.I., Pekhnyo V.I. Peculiarities of formation of novel Rh(III) complex compounds with 2-(2-hydroxybenzoyl)-N-methylhydrazinecarbothioamide. Ukr. Chem. J. 2008. 72 (6): 71-76. (In Ukrainian).
Orysyk S.I., Rybachuk L.N., Pekhnyo V.I., Orysyk V.V. Palladium(II) complexes with 1-allyl-3-(2-pyridyl)thiourea: Synthesis and spectroscopic characterization. Russ. J. Inorg. Chem. 2011. 56(11): 1747–1751.
Orysyk S.I., Bon V.V., Pekhnyo V.I. cis-bis[1-allyl-3-(2-pyridyl-κN) thioureato-κS]palladium(II). Acta Cryst. E. 2009. 65: m1059.
Zborovskii Yu.L., Orysyk V.V., Melnychenko D.O., Orysyk S.I., Repich H.H., Garmanchuk L.V., Palchykovska L.G., Pekhnyo V.I., Vovk M.V. The complexing ability of N-substituted thiourea derivatives as chelating ligands in reaction with Pd(II). J. Org. Pharm. Chem. 2015. 13 (4): 44–49.
Orysyk S.I., Bon V.V., Pekhnyo V.I., Zborovskii Yu.L., Orysyk V.V., Vovk M.V. Synthesis, structure and spectral cha-racteristics of Ni(II), Pd(II) and Zn(II) complexes with N-(2-pyridinyl)morpholine-4-carbothioamide. Polyhedron. 2012. 38: 15–25.
Pearson R.G. Antisymbiosis and the trans effect. Inorg. Chem. 1973. 12 (3): 712–713.
Bon V.V., Orysyk S.I., Pekhnyo, V.I. [Cu3(C11H12N3OS)3(C11H10N3OS)]SO4•3H2O, a trinuclear heteroleptic copper(II) complex with N-allyl-N′-salicylidenethiosemi carbazone and its cyclization product: Synthesis and X-ray diffraction study. Russ. J. Coord. Chem. 2011. 37 (2): 149-152.
Zborovskii Yu.L., Orysyk V.V., Staninets V.I., Rusanov E.B., Chernega A.N. Heterocyclization of N-hetaryl-N′-(prop-2-en-1-yl)thioureas by the action of sulfuryl chloride. Russ. J. Org. Chem. 2007. 43 (7): 1030-1034.
Rybachuk L.N., Repich H.H., Orysyk S.I., Pekhnyo V.I. Complexation of Fe(III), Cu(II), and Cd(II) with N-(pyridin-2-yl)morpholine-4-carbothioamide. Ukr. Chem. J. 2014. 80 (8): 79–83. (In Russian).
Olagunju O., Siegel P.D., Olojo R., Simoyi R.H. Oxyhalogen−sulfur chemistry: Kinetics and mechanism of oxidation of N-acetylthiourea by chlorite and chlorine dioxide. J. Phys. Chem. A. 2006. 110 (7): 2396–2410.
Neverov A.A., Montoya-Pelaez P.J., Brown R.S. Catalysis of the methanolysis of activated amides by divalent and trivalent metal ions. The effect of Zn2+, Co2+ and La3+ on the methanolysis of acetylimidazole and its (NH3)5CoIII complex. J. Am. Chem. Soc. 2001. 123 (2): 210–217.
Cacciapaglia R., Di Stefano S., Kelderman E., Mandolini L., Spadola Fr. Catalysis of anilide ethanolysis by barium and strontium−ethoxide pairs and their complexes with 18-crown-6. J. Org. Chem. 1998. 63 (19): 6476–6479.