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Investigating the reactivity of neutral water-soluble Ru(ii)-PTA carbonyls towards the model imine ligands pyridine and 2,2'-bipyridine.

ABSTRACT: As a continuation of our strategy for preparing new Ru(ii) precursors to be exploited as building blocks in the construction of metal-mediated supramolecular assemblies with improved solubility in water, here we describe the reactivity of selected neutral Ru(ii)-PTA carbonyls (PTA = 1,3,5-triaza-7-phosphaadamantane) towards the model imine ligands pyridine (py) and 2,2'-bipyridine (bpy) and the preparation and characterization of several neutral and cationic water-soluble derivatives: trans,trans,trans-[RuCl₂(CO)(py)(PTA)₂] (7), cis,cis,trans-[RuCl₂(CO)₂(py)(PTA)] (9), cis,trans-[Ru(bpy)Cl(CO)(PTA)₂]Cl (10), mer-[Ru(bpy)(CO)(PTA)₃](Cl)₂ (12), cis,trans-[Ru(bpy)(CO)₂Cl(PTA)]Cl (13), cis,trans-[Ru(bpy)(CO)₂(PTA)₂](NO₃)₂ (14NO₃). In addition, we found that light-induced isomerization in some bpy compounds could be induced. The following species, either side-products isolated in low yield or compounds obtained exclusively in solution, were also unambiguously identified: cis,cis,trans-[RuCl₂(CO)(py)(PTA)₂] (8), trans-[RuCl₂(bpy)(CO)(PTA)] (11), cis,cis-[Ru(bpy)Cl(CO)(PTA)₂]Cl (15) and cis,cis-[Ru(bpy)(CO)₂Cl(PTA)]Cl (16). The X-ray structures of 7, 11·H₂O, and 12·7H₂O are also reported. All compounds are new and - with few exceptions - show a good solubility in water.

SUBMITTER: Battistin F

PROVIDER: S-EPMC9055427 | biostudies-literature | 2020 Jul

REPOSITORIES: biostudies-literature

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Investigating the reactivity of neutral water-soluble Ru(ii)-PTA carbonyls towards the model imine ligands pyridine and 2,2'-bipyridine.

Battistin Federica F Vidal Alessio A Balducci Gabriele G Alessio Enzo E

RSC advances 20200716 45

As a continuation of our strategy for preparing new Ru(ii) precursors to be exploited as building blocks in the construction of metal-mediated supramolecular assemblies with improved solubility in water, here we describe the reactivity of selected neutral Ru(ii)-PTA carbonyls (PTA = 1,3,5-triaza-7-phosphaadamantane) towards the model imine ligands pyridine (py) and 2,2'-bipyridine (bpy) and the preparation and characterization of several neutral and cationic water-soluble derivatives: <i>trans</ ...[more]

PMID: 35515784

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Project description:Cisplatin-based chemotherapy is a common regimen for bladder cancer, a life-threatening cancer with more than 500,000 new cases worldwide annually. Like many other metallodrugs, cisplatin causes severe side effects for its general toxicity. Organoruthenium is known for its structural stability, good anticancer activity, and possible low general toxicity. Here, we have prepared and characterized a series of water-soluble ruthenium-arene complexes with N,N'-chelating ligands: [Ru(II)-η6-arene-(4,4'-(X)2-2,2'-bipyridine)Cl]Cl (arene = p-cymene, X = C4H9 (1), COOH (2), COOCH3 (3), COOC2H5 (4); arene = benzene, X = C4H9 (5), COOCH3 (6), COOC2H5 (7)). These complexes are carefully characterized using single-crystal X-ray diffraction, UV-vis, IR, 1H NMR, and MALDI-TOF MS spectroscopy. Their DFT-calculated structural and thermodynamic properties are consistent with the experimental observations. Biophysicochemical studies of complex interaction with CTDNA and BSA supported by molecular docking simulations reveal suitable properties of 1-7 as anticancer agents. Cytotoxicities of 1-7 are evaluated on healthy human MCF-10a-breast epithelial and African green monkey Vero cells, and carcinoma human HepG-2-hepatic, T24-bladder, and EAhy-926-endothelial cells. All complexes exhibit much higher cytotoxicity for T24 than cisplatin. Particularly, 1 and 2 are also highly selective toward T24. Fluorescence imaging and flow cytometry demonstrate that 1 and 2 penetrate T24 cell membrane and induce early apoptosis at their respective IC50 concentrations, which ultimately lead to cell death. Statistical analysis suggests that the order of importance for T24 cell antiproliferation is protein binding, Log p, Ru-Cl bond length, while DNA binding is the least important. This study is the first to report the anti-bladder cancer efficacy of Ru-arene-2,2'-bipyridine complexes, and may provide insights for rational design of organoruthenium drugs in the enduring search for new chemotherapeutic agents.

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Dataset Information

Investigating the reactivity of neutral water-soluble Ru(ii)-PTA carbonyls towards the model imine ligands pyridine and 2,2'-bipyridine.

Publications

Investigating the reactivity of neutral water-soluble Ru(ii)-PTA carbonyls towards the model imine ligands pyridine and 2,2'-bipyridine.

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