The syntheses of new Pt-II complexes with 4-acyl-5-pyrazolones [HQ(Ph) = 1-phenyl-3-methyl-4-benzoylpyrazol-5-one, a; HQ(py,CF3) = 1-(2-pyridyl)-3-methyl-trifluoroacetylpyrazol-5-one, b] are reported: trans-[PtCl2(DMSO)(HQ(Ph))] (1a), cis-[PtCl2(DMSO)(HQ(Ph))] (2a), [PtCl(DMSO)(Q(py,CF3))] (1b), and [PtCl2(KQ(py,CF3))] (2b). All complexes were characterized by multinuclear (H-1, C-13, F-19, and Pt-195), multidimensional NMR spectroscopy and single-crystal X-ray diffraction analyses. The isomer trans-[PtCl2(DMSO)(HQ(Ph))] (1a) crystallizes in two polymorphic forms, which correspond to two different conformers. In the trans-syn conformer (1a(M)) (monoclinic, space group P2(1)/c), the H atom of the enol group [O(1)H(1)] establishes an intramolecular hydrogen bond with the ketone oxygen (O2), whereas in the trans-anti conformer (1a(O)) (orthorhombic, space group Pca2(1)), the same groups are involved in an analogous intermolecular H bond. Interestingly, the cis isomer (2a) showed in solution and at room temperature slow rotation around both the Pt-N1 and the Pt-S bonds, which restrained both the acylpyrazolone and DMSO ligand motion. Moreover, the water solubility of the complexes trans- and cis-[PtCl2(DMSO)(HQ(Ph))] (1a and 2a) and [PtCl2(KQ(py,CF3))] (2b) allowed to perform in vitro biological assays on platinum-sensitive human endometrium (HeLa) and platinum-resistant human breast (MCF-7) cancer cell lines. It was also possible to compare their cytotoxicity to cisplatin. Interestingly, trans isomer 1a showed higher cytotoxicity on HeLa cells compared to the cis isomer 2a.

Synthesis, Crystal Structure, and Biological Study of PtII Complexes with 4-Acyl-5-pyrazolones / Sandra A. De Pascali; Danilo Migoni; Magda Monari; Claudio Pettinari; Fabio Marchetti; Antonella Muscella; Francesco P. Fanizzi. - In: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. - ISSN 1099-0682. - STAMPA. - 2014:7(2014), pp. 1249-1259. [10.1002/ejic.201301479]

Synthesis, Crystal Structure, and Biological Study of PtII Complexes with 4-Acyl-5-pyrazolones

MONARI, MAGDA;
2014

Abstract

The syntheses of new Pt-II complexes with 4-acyl-5-pyrazolones [HQ(Ph) = 1-phenyl-3-methyl-4-benzoylpyrazol-5-one, a; HQ(py,CF3) = 1-(2-pyridyl)-3-methyl-trifluoroacetylpyrazol-5-one, b] are reported: trans-[PtCl2(DMSO)(HQ(Ph))] (1a), cis-[PtCl2(DMSO)(HQ(Ph))] (2a), [PtCl(DMSO)(Q(py,CF3))] (1b), and [PtCl2(KQ(py,CF3))] (2b). All complexes were characterized by multinuclear (H-1, C-13, F-19, and Pt-195), multidimensional NMR spectroscopy and single-crystal X-ray diffraction analyses. The isomer trans-[PtCl2(DMSO)(HQ(Ph))] (1a) crystallizes in two polymorphic forms, which correspond to two different conformers. In the trans-syn conformer (1a(M)) (monoclinic, space group P2(1)/c), the H atom of the enol group [O(1)H(1)] establishes an intramolecular hydrogen bond with the ketone oxygen (O2), whereas in the trans-anti conformer (1a(O)) (orthorhombic, space group Pca2(1)), the same groups are involved in an analogous intermolecular H bond. Interestingly, the cis isomer (2a) showed in solution and at room temperature slow rotation around both the Pt-N1 and the Pt-S bonds, which restrained both the acylpyrazolone and DMSO ligand motion. Moreover, the water solubility of the complexes trans- and cis-[PtCl2(DMSO)(HQ(Ph))] (1a and 2a) and [PtCl2(KQ(py,CF3))] (2b) allowed to perform in vitro biological assays on platinum-sensitive human endometrium (HeLa) and platinum-resistant human breast (MCF-7) cancer cell lines. It was also possible to compare their cytotoxicity to cisplatin. Interestingly, trans isomer 1a showed higher cytotoxicity on HeLa cells compared to the cis isomer 2a.
2014
Synthesis, Crystal Structure, and Biological Study of PtII Complexes with 4-Acyl-5-pyrazolones / Sandra A. De Pascali; Danilo Migoni; Magda Monari; Claudio Pettinari; Fabio Marchetti; Antonella Muscella; Francesco P. Fanizzi. - In: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. - ISSN 1099-0682. - STAMPA. - 2014:7(2014), pp. 1249-1259. [10.1002/ejic.201301479]
Sandra A. De Pascali; Danilo Migoni; Magda Monari; Claudio Pettinari; Fabio Marchetti; Antonella Muscella; Francesco P. Fanizzi
File in questo prodotto:
Eventuali allegati, non sono esposti

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/464418
 Attenzione

Attenzione! I dati visualizzati non sono stati sottoposti a validazione da parte dell'ateneo

Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 17
  • ???jsp.display-item.citation.isi??? 15
social impact