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The syntheses and spectral (IR, UV-VIS, XPS, and 1H and 13C NMR) characteristics of the rhodium(III), palladium(II), and platinum(II) complexes with 2-(2-hydroxybenzoyl)-N-methylhydrazinecarbothioamide (HBMHCTA) are described. The coordination of HBMHCTA to the central metal ion and its intraligand rearrangement in the complex formation of rhodium(III) ions are studied. The structure of the mixed-ligand complex [Pd(H2L)PPh3] is determined by X-ray diffraction analysis.

A series of novel zinc(II), nickel(II) and palladium(II) complexes with a thiourea derivative (N-(2-pyridinyl)morpholine-4-carbothioamide) (HL) and its oxidation product (N-(2-pyridinyl)morpholine-4-carboxamide) (HL′) have been synthesized and characterized by single crystal X-ray diffraction study, IR, UV–Vis, 1H and 13C NMR spectroscopy. It has been shown that under synthesis conditions, HL coordinates in a thiol tautomeric form leading to formation of mononuclear complexes cis-[ML2], where two ligand molecules are coordinated to metal ions via pyridinyl nitrogen and imidothiolic sulfur in a bidentate manner with the formation of six-membered chelate metallocycles. It has been found that utilizing different conditions nickel complexes are able to crystallize in two polymorphic modifications, which differ solely in the mode of intermolecular interactions. It has been shown that a mixed-ligand complex Ni(C10H13N3O2)2(C2H5SO4)2 can be obtained by reaction of Ni(NO3)2 with reaction by-products (pyridine-containing carboxamide and monoethyl sulfate) formed in selected synthesis conditions.

New Pd(II) complexes with 1-allyl-3-(2-pyridyl)thiourea (APTU) of the formulas [Pd(C9H11N3S)Cl2] (I) and [Pd(C9H11N3S)2]Cl2 (II) were obtained and examined by UV-Vis, IR, and 1H NMR spectroscopy. The conditions for the complexation reactions were optimized. The instability constants and molar absorption coefficients of these complexes were calculated. Comparison of the characteristic bands in the UV-Vis and IR spectra of the complexes and free APTU revealed that the ligand in both complexes is coordinated to the metal atom in the thione form in the bidentate chelating mode through the S atom of the thiourea group and the pyridine N atom. In the UV-Vis spectra of the complexes, the charge transfer bands (π → π* Py) and n → π* (C=NPy), (C=S) experience hypsochromic shifts by 450–470 cm−1 caused by the coordination of APTU to the metal ion, which gives rise to ligand-metal charge-transfer bands (C=NPy → Pd, n → π* (C=S)) and (SPd). The protons in the 6-, 4-, and 3-positions of the pyridine ring and the thiourea NH proton in the chelate ring are most sensitive to the complexation.

Cyclization of 2-(2-{4-[allylamino(thioxo)methyl]piperazin-1-yl}ethyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione by the action of iodine, bromine, or sulfuryl chloride gave 2-(2-{4-[4,5-dihydro-5-(halomethyl)-thiazol-2-yl]piperazin-1-yl}ethyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione hydrohalides which were converted into 2-{2-[4-(5-methylthiazol-2-yl)piperazin-1-yl]ethyl}-1H-benzo[de]isoquinoline-1,3(2H)-dione.

Досліджені реакції комплексоутворення N-заміщених похідних тіосечовини з PdCl2. Встановлено, що функціонально заміщені похідні тіосечовини є ефективними хелатуючими агентами, при цьому природа замісників суттєво впливає на склад і будову комплексних сполук. Так, (N-піридин-2-іл)тіосечовини при взаємодії з PdCl2 утворюють два типи комплексів у співвідношенні M:L 1:1 та 1:2, до складу яких ці реагенти входять як S,N-донорні бідентатні ліганди, координуючись до іона паладію атомом сірки тіонної групи та атомом азоту піридинового ядра. Реакція N-алілтіосечовин із PdCl2 при еквімолярному співвідношенні реагентів приводить до утворення π-комплексів, в яких координація здійснюється за участю атома сірки тіонної групи та С=С подвійного зв’язку алільного фрагмента. Розроблені препаративні методи синтезу такого типу комплексних сполук. Склад синтезованих речовин та спосіб координації лігандів встановлені методами елементного аналізу та 1H ЯМР спектроскопії. Окрім того, будова комплексів 4, 5 доведена рентгеноструктурним методом. Медико-біологічними дослідженнями встановлено, що комплексні сполуки 5 і 6 in vitro проявляють цитостатичну та цитотоксичну дію на пухлинні клітини лінії HeLa., The complexation reactions of N-substituted thiourea derivatives with PdCl2 have been investigated in the present work. The functionally substituted thiourea derivatives are found to be effective chelating agents, in which the nature of substituents has a significant impact to the compositions and structures of complexes. Thus, (N-pyridine-2-yl)thioureas in the interaction with PdCl2 form two types of complexes in the molar ratio of M:L 1:1 and 1:2, in which they act as S,N-bidentate ligands coordinated to the palladium ion by thione sulphur and the nitrogen atom of the pyridine ring. The reaction of N-allylthioureas with PdCl2 in the equimolar ratio results in formation of the π-complexes where the ligands are coordinated by the thione sulphur and the C=C double bond of the allylic moiety. The preparative methods for the synthesis of this type of complexes have been developed. The composition of the products synthesized and the ligands coordination mode have been determined by elemental analysis and 1H NMR spectroscopy. Furthermore, the structure of compounds 4, 5 has been confirmed by the X-ray diffraction study. The biomedical studies have proven that the complex compounds 5 and 6 in vitro have the cytostatic and cytotoxic activity against tumour HeLa cells., Исследованы реакции комплексообразования N-замещенных производных тиомочевины с PdCl2. Установлено, что функционально замещенные производные тиомочевины являются эффективными хелатирующими агентами, при этом природа заместителей существенно влияет на состав и строение комплексных соединений. Так, (N-пиридин-2-ил)тиомочевины при взаимодействии с PdCl2 образуют два типа комплексов в соотношении M:L 1:1 и 1:2, в состав которых эти реагенты входят как S,N-донорные бидентатные лиганды, координируясь к иону палладия атомом серы тионной группы и атомом азота пиридинового ядра. Реакция N-аллилтиомочевин с PdCl2 при эквимолярном соотношении реагентов приводит к образованию π-комплексов, в которых координация осуществляется с участием атома серы тионной группы и С=С двойной связи аллильного фрагмента. Разработаны препаративные методы синтеза этого типа комплексных соединений. Состав синтезированных веществ и способ координации лигандов установлены элементным анализом и методом 1H ЯМР спектроскопии. Кроме того, строение комплексов 4, 5 доказано рентгеноструктурным методом. Медико-биологическими исследованиями установлено, что комплексные соединения 5 и 6 in vitro оказывают цитостатическое и цитотоксическое действие на опухолевые клетки линии HeLa.

Interaction of potassium salts of quinazolin-2-thiol-4-one with γ-substituted allyl halides gave thiazoloquinazolinones with linear or angular structures depending on the structure of the carbonyl radical. S-Allyl substituted quinazolin-2-thiol-4-one reacted with halogens to give iminium salts of thiazinoquinazolinone with an angular structure. The conversion of these salts to the corresponding bases and thiazoloquinazolinones has been studied.

Cyclization of piperazine derivative (III), which contains a fragment intrinsic to antitumor drugs by the action of bromine, iodine, or sulfuryl chloride affords the corresponding hydrohalides.

Reaction of the potassium salt of 2-thioquinazolin-4-one with propargyl halides leads to formation of 2-propargylthioquinazolin-4-one derivatives, which undergo heterocyclization when they are treated with electrophilic or nucleophilic reagents and, depending on the nature of the cyclization agent, leads to formation of tricyclic systems with angular or linear structure.

Interaction of potassium salts of quinazolin-2-thiol-4-one with γ-substituted allyl halides gave thiazoloquinazolinones with linear or angular structures depending on the structure of the carbonyl radical. S-Allyl substituted quinazolin-2-thiol-4-one reacted with halogens to give iminium salts of thiazinoquinazolinone with an angular structure. The conversion of these salts to the corresponding bases and thiazoloquinazolinones has been studied.