Synthesis and characterization of novel palladium(II) complexes of bis(thiosemicarbazone). Structure, cytotoxic activity and DNA binding of Pd(II)-benzyl bis(thiosemicarbazonate) (original) (raw)
Related papers
Bioinorganic Chemistry and Applications, 2013
The palladium(II) bis-chelate complexes of the type [Pd(TSC 1−5 ) 2 ] (6-10), with their corresponding ligands 4-phenyl-1-(acetone)thiosemicarbazone, HTSC 1 (1), 4-phenyl-1-(2 -chloro-benzaldehyde)-thiosemicarbazone, HTSC 2 (2), 4-phenyl-1-(3 -hydroxybenzaldehyde)-thiosemicarbazone, HTSC 3 (3), 4-phenyl-1-(2 -naphthaldehyde)-thiosemicarbazone, HTSC 4 (4), and 4-phenyl-1-(1 -nitro-2 -naphthaldehyde)-thiosemicarbazone, HTSC 5 (5), were synthesized and characterized by elemental analysis and spectroscopic techniques (IR and 1 H-and 13 C-NMR). The molecular structure of HTSC 3 , HTSC 4 , and [Pd(TSC 1 ) 2 ] (6) have been determined by single crystal X-ray crystallography. Complex 6 shows a square planar geometry with two deprotonated ligands coordinated to Pd II through the azomethine nitrogen and thione sulfur atoms in a cis arrangement. The in vitro cytotoxic activity measurements indicate that the palladium(II) complexes (IC 50 = 0.01-9.87 M) exhibited higher antiproliferative activity than their free ligands (IC 50 = 23.48-70.86 and >250 M) against different types of human tumor cell lines. Among all the studied palladium(II) complexes, the [Pd(TSC 3 ) 2 ] (8) complex exhibited high antitumor activity on the DU145 prostate carcinoma and K562 chronic myelogenous leukemia cells, with low values of the inhibitory concentration (0.01 and 0.02 M, resp.).
Journal of the Brazilian Chemical Society, 2010
Três complexos de Pd II com tiossemicarbazonas N(4)-substituídas foram preparados: [Pd(aptsc) (PPh 3 )](NO 3 )•H 2 O, 1, [Pd(apmtsc)(PPh 3 )](NO 3 ), 2, e [Pd(apptsc)(PPh 3 )](NO 3 )•H 2 O, 3, sendo PPh 3 = trifenilfosfina; Haptsc = 2-acetilpyridina-tiossemicarbazona; Hapmtsc = 2-acetilpiridina-N(4)-metil-tiossemicarbazona e Happtsc = 2-acetilpiridina-N(4)-fenil-tiossemicarbazona. Os complexos foram caracterizados por análise elementar, IR, UV-Vis, 1 H e 31 P{ 1 H} NMR e tiveram suas estruturas cristalinas determinadas por difratometria de raios X em monocristal. Os ligantes tiossemicarbazonatos monoaniônicos atuam de modo tridentado, ligando-se ao metal pelos átomos de nitrogênio piridínico, nitrogênio azometínico e enxofre. A atividade citotóxica frente à linhagem de células tumorais MDA-MB231 (tumor de mama) e a atividade anti-Mycobacterium tuberculosis H 37 Rv ATCC 27294 dos compostos foram investigadas. Os complexos de Pd II mostraram-se altamente ativos contra as células tumorais, com valores de IC 50 em torno de 5 μmol L -1 , enquanto o agente antitumoral em uso clínico cisplatina mostrou-se inativo. Os compostos apresentaram atividade anti-M. tuberculosis significante, com valores de CIM comparáveis ou melhores que aqueles referentes a alguns fármacos usados clinicamente contra tuberculose. Three Pd II complexes were prepared from N(4)-substituted thiosemicarbazones: [Pd(aptsc) (PPh 3 )](NO 3 )•H 2 O, 1, [Pd(apmtsc)(PPh 3 )](NO 3 ), 2, and [Pd(apptsc)(PPh 3 )](NO 3 )•H 2 O, 3,
Journal of Inorganic Biochemistry, 2007
The preparation of new palladium(II) and platinum(II) complexes derived from a-diphenyl ethanedione bis(thiosemicarbazone), 1, and a-diphenyl ethanedione bis(4-ethylthiosemicarbazone), 2, is described. The palladium complexes 3 and 4 and platinum complexes 5 and 6 have been characterized by elemental analyses, fast atom bombardment mass spectrometry (FAB + ) and spectroscopic studies (IR, 1 HNMR). The crystal and molecular structures of the dimeric cyclopalladated compound 4 and the mononuclear platinum complex 6 have been determined by single crystal X-ray diffraction. The cytotoxic activity of the free ligands and palladium and platinum complexes against human A2780 and A2780cisR (acquired resistance to cisplatin) epithelial ovarian carcinoma cells lines is also reported. The IC 50 values for compounds 1, 5 and 6 were found to be higher than that of cisplatin but the maximum antiproliferative activity was similar. Furthermore, the compounds largely retain their activity in the A2780cisR cell line, having a much better resistance factor than cisplatin in the pair of cell lines tested.
Bioinorganic Chemistry and Applications, 2008
The palladium (II) bis-chelate Pd (L 1−3 ) 2 and platinum (II) tetranuclear Pt 4 (L 4 ) 4 complexes of benzaldehyde thiosemicarbazone derivatives have been synthesized, and characterized by elemental analysis and IR, FAB(+)-mass and NMR ( 1 H, 13 C) spectroscopy. The complex Pd(L 2 ) 2 [HL 2 = m-CN-benzaldehyde thiosemicarbazone] shows a square-planar geometry with two deprotonated ligands (L) coordinated to Pd II through the nitrogen and sulphur atoms in a transarrangement, while the complex Pt 4 (L 4 ) 4 [HL 4 = 4-phenyl-1-benzaldehyde thiosemicarbazone] has a tetranuclear geometry with four tridentate ligands coordinated to four Pt II ions through the carbon (aromatic ring), nitrogen, and sulphur atoms where the ligands are deprotonated at the NH group. The in vitro antitumor activity of the ligands and their complexes was determined against different human tumor cell lines, which revealed that the palladium (II) and platinum (II) complexes are more cytotoxic than their ligands with IC 50 values at the range of 0.07-3.67 μM. The tetranuclear complex Pt 4 (L 4 ) 4 , with the phenyl group in the terminal amine of the ligand, showed higher antiproliferative activity (CI 50 = 0.07-0.12 μM) than the other tested palladium (II) complexes.
European Journal of Medicinal Chemistry, 2008
New complexes of Pd(II) with N-substituted thiosemicarbazone (1)e(3) have been synthesised and characterised by elemental analyses, IR, electronic, 1 H NMR spectroscopies. The electrochemical behaviour of the complexes has been tested by using cyclic voltammetry. The crystal structures of the complexes have been determined by single crystal X-ray diffraction technique. In all the complexes the thiosemicarbazone ligand is coordinated to palladium through ONS mode. The complex 1 crystallises in the monoclinic space group P2 1 /c with two molecules per unit cell, has the dimensions of a ¼ 9.4390(19) Å , b ¼ 10.645(2) Å , c ¼ 13.668(3) Å , a ¼ 90 , b ¼ 91.43 and g ¼ 90. The complex 3 crystallises in the monoclinic space group P2 1 /c with four molecules per unit cell, has the dimensions of a ¼ 14.119(3) Å , b ¼ 11.155(2) Å , c ¼ 18.503(4) Å , a ¼ 90 , b ¼ 112.02 and g ¼ 90. The new complexes have been tested for their antibacterial activity against various pathogenic bacteria. From this study, it was found out that the activity of the complex 2 almost reaches the effectiveness of the conventional bacteriocide Streptomycin.
International Journal of Molecular Sciences
The current research describes the synthesis and characterization of 2-acetylpyridine N(4)-cyclohexyl-thiosemicarbazone ligand (HL) and their two metal complexes, [Au(L)Cl][AuCl2] (1) and [Pd(L)Cl]·DMF (2). The molecular structures of the compounds were determined by physicochemical and spectroscopic methods. Single crystal X-ray diffraction was employed in the structural elucidation of the new complexes. The complexes showed a square planar geometry to the metal center Au(III) and Pd(II), coordinated with a thiosemicarbazone molecule by the NNS-donor system and a chloride ion. Complex (1) also shows the [AuCl2]− counter-ion in the asymmetric unit, and complex (2) has one DMF solvent molecule. These molecules play a key role in the formation of supramolecular structures due to different interactions. Noncovalent interactions were investigated through the 3D Hirshfeld surface by the dnorm function and the 2D fingerprint plots. The biological activity of the compounds was evaluated in...
Journal of Inorganic Biochemistry, 1988
Complexes of Mn(II), Fe(III), Fe(II), Co(II), Ni(II), Cu(II), Zn(II) and Pt(II) with 2,6-diacetylpyridine bis(N4-azacyclic thiosemicarbazones), abbreviated as H2L, have been prepared and characterized by elemental analysis, molar conductance, magnetic moments (300-78 K) and spectral studies. On the basis of these studies, a distorted six-coordinate structure for Fe(L)Cl and a distorted five-coordinate structure for M(L) (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), or Pt(II] are suggested. The ligands undergo deprotonation and appear to coordinate through the thione sulphur, the imine nitrogen and pyridyl nitrogen. All the ligands and metal complexes were screened for their antitumor activity against P 388 lymphocytic leukemia test system in mice, and it was found that a few of them possess significant activity at the dosages used.
Cytotoxic properties of two families of benzaldehyde thiosemicarbazone complexes of palladium
Zenodo (CERN European Organization for Nuclear Research), 2013
Reaction of 4-R-benzaldehy~e thiosernicarbazones (HL-R, where H stands for the dissociable hydrazinic proton-and R (R = OCH 3 , CH 3 , H, Cl and N0 2) for the substituent) with trans-[Pd(PPh 3) 2 CI 2 ] and Na 2 [PdCI 4 ] afford complexes of type [Pd(PPh 3)(L-R)CI] and [Pd(L-R) 2 ] respectively. In vitro cytotoxicity screenings of these complexes along with four human clinical drugs, viz. cisplatin, BCNU, 5-fluorouracil (5-FU) and hydtoxyurea, have been carried out in two human tumor cell lines, viz. pro myelocytic leukemia HL-60 and histiocytic lymphoma U-937. Majority of these complexes show remarkably low IC50 value and are found to be much more cytotoxic than the reference anticancer drugs in both the cell lines. Apoptosis study in HL-60 with two selected complexes from each group shows that at 5 and 10 JLM concentration they induce apoptosis to a greater extent than cisplatin and camptothecin.
Journal of Chemistry
In a bid to come up with potential anticancer agents, a class of thiosemicarbazone ligands bearing substituted thiophene were synthesized followed by complexation with various Pd(II) and Pt(II) metal precursors. The ligands (E)-1-((thiophen-2-yl)methylene)thiosemicarbazide (L1), (E)-1-((4-bromothiophen-2-yl)methylene)thiosemicarbazide (L2), and (E)-1-((5-bromothiophen-2-yl)methylene)thiosemicarbazide (L3) were synthesized by condensation reactions and obtained in good yields. Complexation of L1 and L2 with Pd(cod)Cl2 gave C1 (C6H7Cl2N3PdS2) and C2 (C6H6BrCl2N3PdS2), respectively. Complexation of L1 with K2PtCl4 gave C3 (C6H7Cl2N3PtS2), while L3 with K2PtCl2[(PPh)3]2 gave C4 (C24H21BrClN3PPtS2). The structures and coordination for all compounds were established by FTIR, 1H-NMR, 13C-NMR, UV-Vis, elemental analysis, and single-crystal X-ray diffraction studies for ligand L1. Tuning of the spectral and anticancer activity of the compounds was investigated by changing the position of the...