The β-diketonate ligands hold an important place in the history of coordination chemistry and continue to be among the most ubiquitous ligands for use as catalysts, pre-catalysts, NMR shift reagents and biochemically active agents. β-diketones are known to form complexes with almost every metal, and they have been used as supporting ligands for Ti(IV), Ru(II), Pd(II) and Pt-based anticancer agents. In particular, several Pt(II) complexes with β-diketonate ligands as leaving groups were studied, revealing that the ligands play an integral role in modulating toxic side effects. In particular, the phenyl ring substituents increase the lipophilicity and improve cellular uptake of the resulting complexes, whereas the electron-withdrawing CF3 groups increase the hydrolysis rates of the complexes in aqueous solution. Therefore, as part of our continuous investigation on the chemical and biological properties of metal-based coordination compounds, we report here a study on the syntheses, characterization, and biological evaluation of new homoleptic ([ML2]; M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)) and heteroleptic ([ML(PR3)n]; M = Cu(I) or Ag(I); PR3 = PR3 or PTA) metal-complexes supported by the anion of sterically hindered β-diketonate ligands, 1,3-dimesitylpropane-1,3-dione (HLMes) and the 1,3-bis(3,5-bis(trifluoromethyl)phenyl)-3-hydroxyprop-2-en-1-one (HLCF3) characterized by the presence of fluorinated or methyl groups on the phenyl moieties. A particular attention was devoted to the synthesis of copper(II) and copper(I) species, also in view of their biological activity as potential antiviral and anticancer agents.
Design, synthesis and biological properties of novel first-row transition metal complexes supported by sterically hindered β-diketonate ligands
Jo Del Gobbo
;Maura Pellei;Miriam Caviglia;Carlo Santini
2023-01-01
Abstract
The β-diketonate ligands hold an important place in the history of coordination chemistry and continue to be among the most ubiquitous ligands for use as catalysts, pre-catalysts, NMR shift reagents and biochemically active agents. β-diketones are known to form complexes with almost every metal, and they have been used as supporting ligands for Ti(IV), Ru(II), Pd(II) and Pt-based anticancer agents. In particular, several Pt(II) complexes with β-diketonate ligands as leaving groups were studied, revealing that the ligands play an integral role in modulating toxic side effects. In particular, the phenyl ring substituents increase the lipophilicity and improve cellular uptake of the resulting complexes, whereas the electron-withdrawing CF3 groups increase the hydrolysis rates of the complexes in aqueous solution. Therefore, as part of our continuous investigation on the chemical and biological properties of metal-based coordination compounds, we report here a study on the syntheses, characterization, and biological evaluation of new homoleptic ([ML2]; M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)) and heteroleptic ([ML(PR3)n]; M = Cu(I) or Ag(I); PR3 = PR3 or PTA) metal-complexes supported by the anion of sterically hindered β-diketonate ligands, 1,3-dimesitylpropane-1,3-dione (HLMes) and the 1,3-bis(3,5-bis(trifluoromethyl)phenyl)-3-hydroxyprop-2-en-1-one (HLCF3) characterized by the presence of fluorinated or methyl groups on the phenyl moieties. A particular attention was devoted to the synthesis of copper(II) and copper(I) species, also in view of their biological activity as potential antiviral and anticancer agents.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
