Synthesis, Characterization, and Cytotoxicity Studies of N-(4-Methoxybenzyl) Thiosemicarbazone Derivatives and Their Ruthenium(II)-<i>p</i>-cymene Complexes
The reaction of [Ru<sub>2</sub>Cl<sub>2</sub>(μ-Cl)<sub>2</sub>(η<sup>6</sup>-<i>p</i>-cymene)<sub>2</sub>] with two thiosemicarbazones obtained by the condensation of N-(4-methoxybenzyl) thiosemicarbazide and 1,4-hydroxy-3-meth...
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MDPI AG
2022-11-01
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| Online Access: | https://www.mdpi.com/1420-3049/27/22/7976 |
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| author | Mónica Martínez-Estévez Soledad García-Fontán Saray Argibay-Otero Inmaculada Prieto Ezequiel M. Vázquez-López |
| author_facet | Mónica Martínez-Estévez Soledad García-Fontán Saray Argibay-Otero Inmaculada Prieto Ezequiel M. Vázquez-López |
| author_sort | Mónica Martínez-Estévez |
| collection | DOAJ |
| description | The reaction of [Ru<sub>2</sub>Cl<sub>2</sub>(μ-Cl)<sub>2</sub>(η<sup>6</sup>-<i>p</i>-cymene)<sub>2</sub>] with two thiosemicarbazones obtained by the condensation of N-(4-methoxybenzyl) thiosemicarbazide and 1,4-hydroxy-3-methoxyphenyl)ethan-1-one (<b>HL<sup>1</sup></b>) or 2-fluoro-4-hydroxybenzaldehyde (<b>HL<sup>2</sup></b>) was studied. The cationic complexes of formula [RuCl(η<sup>6</sup>-<i>p</i>-cymene)(HL)]<sup>+</sup> were isolated as solid chloride and trifluoromethylsulfate (TfO) salts. A study of the solid state and NMR spectra suggests the presence in the material of two isomers that differ in the configuration in the iminic bond, C2=N3, of the coordinated thiosemicarbazone in the triflate salts and only the <i>E</i> isomer in the chloride. An X-ray study of single crystals of the complexes supports this hypothesis. The thiosemicarbazone ligand coordinates with the ruthenium center through the iminic and sulfur atoms to form a five-membered chelate ring. Furthermore, the isolation of single crystals containing the thiosemicarbazonate complex [Ru<sub>2</sub>(μ-L<sup>2</sup>)<sub>2</sub>(η<sup>6</sup>-<i>p</i>-cymene)<sub>2</sub>]<sup>2+</sup> suggests the easy labilization of the coordinated chloride in the complex. The redox behavior of the ligands and complexes was evaluated by cyclic voltammetry. It seems to be more difficult to oxidize the complex derived from HL<sup>1</sup> than HL<sup>2</sup>. The ability of the complexes to inhibit cell growth against the NCI-H460, A549 and MDA-MB-231 lines was evaluated. The complexes did not show greater potency than cisplatin, although they did have greater efficacy, especially for the complex derived from <b>HL<sup>1</sup></b>. |
| first_indexed | 2024-03-09T18:07:17Z |
| format | Article |
| id | doaj.art-b2495d1f327a4db0afbc95fdeb39861e |
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| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T18:07:17Z |
| publishDate | 2022-11-01 |
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| spelling | doaj.art-b2495d1f327a4db0afbc95fdeb39861e2023-11-24T09:24:18ZengMDPI AGMolecules1420-30492022-11-012722797610.3390/molecules27227976Synthesis, Characterization, and Cytotoxicity Studies of N-(4-Methoxybenzyl) Thiosemicarbazone Derivatives and Their Ruthenium(II)-<i>p</i>-cymene ComplexesMónica Martínez-Estévez0Soledad García-Fontán1Saray Argibay-Otero2Inmaculada Prieto3Ezequiel M. Vázquez-López4Departamento de Química Inorgánica, Campus Universitario, Universidade de Vigo, E-36310 Vigo, SpainDepartamento de Química Inorgánica, Campus Universitario, Universidade de Vigo, E-36310 Vigo, SpainDepartamento de Química Inorgánica, Campus Universitario, Universidade de Vigo, E-36310 Vigo, SpainMetallosupramolecular Chemistry Group, Galicia South Health Research Institute (IIS Galicia Sur) SERGAS-UVIGO, E-36213 Vigo, SpainDepartamento de Química Inorgánica, Campus Universitario, Universidade de Vigo, E-36310 Vigo, SpainThe reaction of [Ru<sub>2</sub>Cl<sub>2</sub>(μ-Cl)<sub>2</sub>(η<sup>6</sup>-<i>p</i>-cymene)<sub>2</sub>] with two thiosemicarbazones obtained by the condensation of N-(4-methoxybenzyl) thiosemicarbazide and 1,4-hydroxy-3-methoxyphenyl)ethan-1-one (<b>HL<sup>1</sup></b>) or 2-fluoro-4-hydroxybenzaldehyde (<b>HL<sup>2</sup></b>) was studied. The cationic complexes of formula [RuCl(η<sup>6</sup>-<i>p</i>-cymene)(HL)]<sup>+</sup> were isolated as solid chloride and trifluoromethylsulfate (TfO) salts. A study of the solid state and NMR spectra suggests the presence in the material of two isomers that differ in the configuration in the iminic bond, C2=N3, of the coordinated thiosemicarbazone in the triflate salts and only the <i>E</i> isomer in the chloride. An X-ray study of single crystals of the complexes supports this hypothesis. The thiosemicarbazone ligand coordinates with the ruthenium center through the iminic and sulfur atoms to form a five-membered chelate ring. Furthermore, the isolation of single crystals containing the thiosemicarbazonate complex [Ru<sub>2</sub>(μ-L<sup>2</sup>)<sub>2</sub>(η<sup>6</sup>-<i>p</i>-cymene)<sub>2</sub>]<sup>2+</sup> suggests the easy labilization of the coordinated chloride in the complex. The redox behavior of the ligands and complexes was evaluated by cyclic voltammetry. It seems to be more difficult to oxidize the complex derived from HL<sup>1</sup> than HL<sup>2</sup>. The ability of the complexes to inhibit cell growth against the NCI-H460, A549 and MDA-MB-231 lines was evaluated. The complexes did not show greater potency than cisplatin, although they did have greater efficacy, especially for the complex derived from <b>HL<sup>1</sup></b>.https://www.mdpi.com/1420-3049/27/22/7976rutheniummetallocenethiosemicarbazonecytotoxicity |
| spellingShingle | Mónica Martínez-Estévez Soledad García-Fontán Saray Argibay-Otero Inmaculada Prieto Ezequiel M. Vázquez-López Synthesis, Characterization, and Cytotoxicity Studies of N-(4-Methoxybenzyl) Thiosemicarbazone Derivatives and Their Ruthenium(II)-<i>p</i>-cymene Complexes Molecules ruthenium metallocene thiosemicarbazone cytotoxicity |
| title | Synthesis, Characterization, and Cytotoxicity Studies of N-(4-Methoxybenzyl) Thiosemicarbazone Derivatives and Their Ruthenium(II)-<i>p</i>-cymene Complexes |
| title_full | Synthesis, Characterization, and Cytotoxicity Studies of N-(4-Methoxybenzyl) Thiosemicarbazone Derivatives and Their Ruthenium(II)-<i>p</i>-cymene Complexes |
| title_fullStr | Synthesis, Characterization, and Cytotoxicity Studies of N-(4-Methoxybenzyl) Thiosemicarbazone Derivatives and Their Ruthenium(II)-<i>p</i>-cymene Complexes |
| title_full_unstemmed | Synthesis, Characterization, and Cytotoxicity Studies of N-(4-Methoxybenzyl) Thiosemicarbazone Derivatives and Their Ruthenium(II)-<i>p</i>-cymene Complexes |
| title_short | Synthesis, Characterization, and Cytotoxicity Studies of N-(4-Methoxybenzyl) Thiosemicarbazone Derivatives and Their Ruthenium(II)-<i>p</i>-cymene Complexes |
| title_sort | synthesis characterization and cytotoxicity studies of n 4 methoxybenzyl thiosemicarbazone derivatives and their ruthenium ii i p i cymene complexes |
| topic | ruthenium metallocene thiosemicarbazone cytotoxicity |
| url | https://www.mdpi.com/1420-3049/27/22/7976 |
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