Artículo
Steric and Electronic Effects Responsible for N, O- or N, N-Chelating Coordination of Pyrazolones Containing a Pyridine Ring in Ruthenium Arene Systems
Autor/es | Pietracci, Lorenzo
Pettinari, Riccardo Tombesi, Alessia Marchetti, Fabio Pettinari, Claudio Galindo del Pozo, Agustín Fadaei-Tirani, Farzaneh Hadiji, Mouna Dyson, Paul J. |
Departamento | Universidad de Sevilla. Departamento de Química Inorgánica |
Fecha de publicación | 2023 |
Fecha de depósito | 2024-05-10 |
Publicado en |
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Resumen | Structural and electronic factors are crucial to rationalize the different N,O or N,N chelating coordination of pyrazolones containing a pyridine ring. The reactivity of proligand 3-phenyl-1-(pyridin-2-yl)-5-pyrazolone ... Structural and electronic factors are crucial to rationalize the different N,O or N,N chelating coordination of pyrazolones containing a pyridine ring. The reactivity of proligand 3-phenyl-1-(pyridin-2-yl)-5-pyrazolone (HLpy,ph) with the (arene)Ru(II) fragment was explored. Neutral and ionic (arene)Ru(II) complexes were obtained and fully characterized, also by X-ray diffraction, revealing the ligand to coordinate in an unusual N,O-chelating fashion. Other ruthenium complexes were also synthesized with 3-methyl-1-(pyridin-2-yl)-5-pyrazolone (HLpy,me) and 3-methyl-1-(pyridin-2-yl)-4-trifluoroacetyl-5-pyrazolone (HQpy,CF3). In these complexes the ligands adopt the preferred N,N-chelating mode. Ligands and complexes were theoretically analyzed by density functional theory (DFT). The most stable tautomer of HLpy,phmatched well with the experimental behavior of this proligand and the structures of Ru-complexes were well described by calculations. The thermodynamic stability of the N,O- and N,N-coordination modes was analyzed and a proposal for the achievement of the N,O-coordination mode in complexes 1-4 was proposed. Cytotoxicity tests were performed against human ovarian carcinoma (A2780 and Cisplatin-resistant A2780cis) and nontumorigenic human embryonic kidney (HEK293T) cell lines, showing the free ligands to be more cytotoxic that the ensuing (arene)Ru(II) complexes. |
Cita | Pietracci, L., Pettinari, R., Tombesi, A., Marchetti, F., Pettinari, C., Galindo del Pozo, A.,...,Dyson, P.J. (2023). Steric and Electronic Effects Responsible for N, O- or N, N-Chelating Coordination of Pyrazolones Containing a Pyridine Ring in Ruthenium Arene Systems. Organometallics, 42 (13), 1495-1504. https://doi.org/10.1021/acs.organomet.3c00121. |
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