Arene-ruthenium(II) complexes with pyrazole-based ligands bearing a pyridine moiety: Synthesis, structure, DFT calculations, and cytotoxicity

Pettinari, Riccardo; Marchetti, Fábio; Tombesi, Alessia; Nicola, Corrado Di; Pettinari, Cláudio; Guo, Chuanpan; Galindo, Agustı́n; Fadaei‐Tirani, Farzaneh; Hadiji, Mouna; Dyson, Paul J.

doi:10.1016/j.ica.2021.120610

Cited by 9 publications

(16 citation statements)

References 43 publications

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“… This confirms the appropriateness of the selected combination of method and basis sets. As previously noted for the related proligand HL py,me , the existence in rotamer I-r of an intramolecular hydrogen bond (O–H···N, 1.781 Å; O···N, 2.649 Å; and O–H···N angle of 144.2°) is the key stabilizing factor. Complexes 1 – 4 were also studied by DFT calculations.…”

Section: Resultsmentioning

confidence: 99%

“…The ligands HL py,me and HQ py,CF3 were synthesized by a procedure similar to that previously reported. 6 IR spectra were recorded on a PerkinElmer Frontier FT-IR instrument.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…Complex 5 was prepared from [Ru(cym)(L py,me )Cl], previously reported. 6 82.4 mg (0.15 mmol) of the starting complex were dissolved in 30 mL of methanol and it was added to 1 mL of an aqueous solution of AgBF 4 (98% of purity) (29.8 mg, 0.15 mmol). PTA (97% of purity) was added (24.3 (6).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…Complex 8 was prepared using a method similar to that of 7 from [Ru(hmb)(Q py,CF3 )Cl], previously reported. 6 96.1 mg (0.17 mmol) of the starting complex were dissolved in 30 mL of methanol and an aqueous solution (1 mL) of AgPF 6 (43.0 mg, 0.17 mmol) was added. Then, 27.5 mg (0.17 mmol) of PTA (97% of purity) was added and the solution was stirred for 2 h. AgCl was formed as byproduct, and it was filtered.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…3−5 Recently, we expanded our studies on arene-Ru(II) chemistry of two proligands, namely 3-methyl-1-(pyridin-2-yl)-5-pyrazolone (HL py,me ) and 3-methyl-1-(pyri-din-2-yl)-4-trifluoroacetyl-5-pyrazolone (HQ py,CF3 , Chart 2). 6 The two ligands were found able to coordinate (in the deprotonated form) to Ru(II) in a bidentate N,N-fashion, 6 which is structurally analogous to some very cytotoxic Ru(II)and Os(II)-arene phenylazopyridine complexes. 7 Both proligands and their neutral arene-Ru(II) complexes (arene = cymene and hexamethylbenzene) were tested against A2780 and A2780cis tumor cell lines and compared to HEK293T nontumor cell lines, giving some promising results.…”

Section: ■ Introductionmentioning

confidence: 99%

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Steric and Electronic Effects Responsible for N,O- or N,N-Chelating Coordination of Pyrazolones Containing a Pyridine Ring in Ruthenium Arene Systems

Pietracci,

Pettinari,

Tombesi

et al. 2023

Organometallics

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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,ph matched 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.

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Section: Resultsmentioning

confidence: 99%

“…The ligands HL py,me and HQ py,CF3 were synthesized by a procedure similar to that previously reported. 6 IR spectra were recorded on a PerkinElmer Frontier FT-IR instrument.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Steric and Electronic Effects Responsible for N,O- or N,N-Chelating Coordination of Pyrazolones Containing a Pyridine Ring in Ruthenium Arene Systems

Pietracci,

Pettinari,

Tombesi

et al. 2023

Organometallics

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Organometallic (η⁶‐p‐cymene)ruthenium(II) complexes with thiazolyl‐based organic twigs: En route towards targeted delivery via human serum albumin of the potential anticancer agents

Khan

BinSharfan

Alterary

et al. 2021

Applied Organom Chemis

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In this article, we have designed the new ruthenium(II) p‐cymene complexes [Ru(η6‐p‐cymene) HLThz,Me Cl] 1 and [Ru(η6‐p‐cymene) HLThz Cl] 2 with two auxiliary ligand (E)‐1‐(((5‐methylthiazol‐2‐yl)imino)methyl)naphthalen‐2‐ol (HLThz,Me) and (E)‐1‐((thiazol‐2‐ylimino)methyl)naphthalen‐2‐ol (HLThz), keeping in mind the vehicle HSA. The spectroscopic techniques, namely, Fourier transform infrared spectroscopy (FT‐IR), proton nuclear magnetic resonance (1H NMR), 13C NMR, and elemental analysis were employed for the characterization. The single X‐ray crystallography ascertains the molecular structure of the representative complex [Ru(η6‐p‐cymene) HLThz,Me Cl] 1. Furthermore, the density functional theory (DFT) calculation was performed for geometry optimization and frontier molecular orbitals analysis. Moreover, in silico studies were carried out to understand the binding site and the mode of interaction of the complexes with human serum albumin (HSA). The in vitro interaction of the HSA measured extrinsic fluorescence at various temperatures, namely, 298, 303, and 308 K, whereas the intrinsic fluorescence extent was evaluated in the presence of 8‐anilinonaphthalene‐1‐sulfonic acid (ANS). The cytotoxicity of these compounds was evaluated against HeLa, MCF7, HepG2, A549, and A2780 cancer cells and compared with HEK293 non‐tumorigenic cells (cisplatin and RAPTA‐C as control). The complex 1 showed significantly good cytotoxicity in the range of IC50 value <10 μM against A2780 (ovarian cancer) and HepG2 (liver) cells and lower toxicity up to >100 μM. These findings give illustrative insight into the binding propensity of complexes 1 and 2 with HSA (model protein). Further, they can be explored for en route drug delivery to a specific site as anticancer metallodrugs.

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A Computational approach toward organometallic ruthenium(II) compounds with tunable hydrolytic properties

Kuznetsov

Thomet

2022

Chemical Physics

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Arene-ruthenium(II) complexes with pyrazole-based ligands bearing a pyridine moiety: Synthesis, structure, DFT calculations, and cytotoxicity

Cited by 9 publications

References 43 publications

Steric and Electronic Effects Responsible for N,O- or N,N-Chelating Coordination of Pyrazolones Containing a Pyridine Ring in Ruthenium Arene Systems

Steric and Electronic Effects Responsible for N,O- or N,N-Chelating Coordination of Pyrazolones Containing a Pyridine Ring in Ruthenium Arene Systems

Organometallic (η⁶‐p‐cymene)ruthenium(II) complexes with thiazolyl‐based organic twigs: En route towards targeted delivery via human serum albumin of the potential anticancer agents

A Computational approach toward organometallic ruthenium(II) compounds with tunable hydrolytic properties

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Arene-ruthenium(II) complexes with pyrazole-based ligands bearing a pyridine moiety: Synthesis, structure, DFT calculations, and cytotoxicity

Cited by 9 publications

References 43 publications

Steric and Electronic Effects Responsible for N,O- or N,N-Chelating Coordination of Pyrazolones Containing a Pyridine Ring in Ruthenium Arene Systems

Steric and Electronic Effects Responsible for N,O- or N,N-Chelating Coordination of Pyrazolones Containing a Pyridine Ring in Ruthenium Arene Systems

Organometallic (η6‐p‐cymene)ruthenium(II) complexes with thiazolyl‐based organic twigs: En route towards targeted delivery via human serum albumin of the potential anticancer agents

A Computational approach toward organometallic ruthenium(II) compounds with tunable hydrolytic properties

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Organometallic (η⁶‐p‐cymene)ruthenium(II) complexes with thiazolyl‐based organic twigs: En route towards targeted delivery via human serum albumin of the potential anticancer agents