Facile entry to germanate and stannate complexes [(η6-arene)RuCl(η2-dppm)]+[ECl3]- (E = Ge, Sn) as potent anti-cancer agents

Aldeghi, Niccolo; Romano, Dario; Marschner, Christoph; Biswas, Supratim; Chakraborty, Suparna; Prince, Sharon; Ngubane, Siyabonga; Blom, Burgert

doi:10.1016/j.jorganchem.2020.121214

Cited by 9 publications

(7 citation statements)

References 59 publications

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“…The germanate anion is separated from the cation and is thus a separated ion pair. It exhibits trigonal pyramidal geometry in close similarity to its Ru analogue reported by us earlier …”

Section: Resultssupporting

confidence: 84%

“…We have reported a series of neutral ruthenium-based germyl ([Ru]–GeCl 3 ) and stannyl ([Ru]–SnCl 3 ) complexes that displayed less than optimal cytotoxic activity on numerous cell lines in vitro (Scheme ). , In contrast, ruthenium germanate and stannate salt complexes displayed potent and promising cytotoxic activity on two breast cancer cell lines (MCF-7 and MDA-MB-231) and good selectivity, suggesting that the ionic nature of the complexes influences their biological effects …”

Section: Introductionmentioning

confidence: 99%

“…The anticancer or biological activity investigations of any of these four classes of compounds or elucidations of their bonding nature by theoretical methods have not previously been evaluated. Moreover, given our previous numerous studies on ruthenium arene stannyl and stannate complexes, as well as their germanium analogues, ,, the extension to osmium is expected to yield different biological activities given the rather inert nature of Os(II) vs Ru(II) (see above). This hence motivated us to explore the analogous osmium chemistry with a view of biological anticancer applications, not as a mere extension from Ru, but expecting different in vitro biological activities compared to analogous ruthenium complexes.…”

Section: Introductionmentioning

confidence: 99%

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Osmium Arene Germyl, Stannyl, Germanate, and Stannate Complexes as Anticancer Agents

et al. 2021

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Herein, we describe the synthesis, full spectroscopic characterization, DFT (density functional theory) calculations, and single-crystal X-ray diffraction analyses of a series of osmium arene σ-germyl, germanate, σ-stannyl, and stannate complexes, along with their cytotoxic (anticancer) investigations. The known dimer complexes [OsCl2(η6-C6H6)]2 (1) and [OsCl2(η6-p-cymene)]2 (2) were reacted with PPh3 to form the known mononuclear complex [OsCl2(η6-p-cymene)(PPh3)] (3) and the new complex [OsCl2(η6-C6H6)(PPh3)] (6); complex 3 was reacted with GeCl2·(dioxane) and SnCl2 to afford, by insertion into the Os–Cl bond, the neutral σ-germyl and stannyl complexes [OsCl(η6-p-cymene)(PPh3)(GeCl3)] (7) and [OsCl(η6-p-cymene)(PPh3)(SnCl3)] (11), respectively, as a mixture of enantiomers. Similarly, the reaction of complex 6 with GeCl2·(dioxane) afforded [OsCl(η6-C6H6)(PPh3)(GeCl3)] (9). Complex 2, upon reaction with 1,1-bis(diphenylphosphino)methane (dppm), formed a mixture of [OsCl2(η6-p-cymene)(κ1-dppm)] (4) and [Os(η6-p-cymene)(κ2-dppm)Cl]+Cl– (5) when prepared in acetonitrile and a mixture of 4 and the dinuclear complex [[OsCl2(η6-p-cymene)]2(μ-dppm)] (0) when prepared in dichloromethane. By utilizing either isolated 4 or a mixture of 4 and 5, the synthesis of κ2-dppm germanate and stannate salts, [OsCl(η6-p-cymene)(κ2-dppm)]+GeCl3 – (8) and [OsCl(η6-p-cymene)(κ2-dppm)]+SnCl3 – (10), were accomplished via halide-abstracting reactions with GeCl2·(dioxane) or SnCl2, respectively. All resulting complexes were characterized by means of multinuclear NMR, FT-IR, ESI-MS, and UV/Vis spectroscopy. X-ray diffraction analyses of 4, 8, 9, 10, and 11 were performed and are reported. DFT studies (B3LYP, basis set LANL2DZ for Os, and def2-TZVPP for Sn, Ge, Cl, P, C, and H) were performed on complex 9 and the benzene analogue of complex 11, 11–benzene, to evaluate the structural changes and the effects on the frontier molecular orbitals arising from the substitution of Ge for Sn. Finally, complexes 3 and 7–11 were investigated for potential anticancer activities considering cell cytotoxicity and apoptosis assays against Dalton’s lymphoma (DL) and Ehrlich ascites carcinoma (EAC) malignant cancer cell lines. The complexes were also tested against healthy peripheral blood mononuclear cells (PBMCs). All cell lines were also treated with the reference drug cisplatin to draw a comparison with the results obtained from the reported complexes. The study was further corroborated with in silico molecular interaction simulations and a pharmacokinetic study.

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“…The germanate anion is separated from the cation and is thus a separated ion pair. It exhibits trigonal pyramidal geometry in close similarity to its Ru analogue reported by us earlier …”

Section: Resultssupporting

confidence: 84%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Osmium Arene Germyl, Stannyl, Germanate, and Stannate Complexes as Anticancer Agents

et al. 2021

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“…59 Additionally, sterically demanding tertiary phosphines, such as bis(diphenylphosphino)alkanes, tend to promote monodentate bonding. [59][60][61] Moreover, the length of the alkane chain in these ligands can have a pronounced effect on the interaction between the two metals -and, therefore, the chemical and biological activity of the complex -allowing for further fine-tuning of the system for biological applications. 59 Indeed, a recent review describes developments in the field of bimetallic systems bridged bybis(diphenylphopshino)methane, with data suggesting that the incorporation of two distinct metal centres in a heterobimetallic system can enhance cytotoxicity compared to homobimetallic analogues.…”

Section: Introductionmentioning

confidence: 99%

“…Initial investigations focused on half-sandwich Ru(II)-arene complexes bearing stannyl and germyl ligands. [61][62][63] While the cytotoxicity of these complexes as suboptimal, results suggested that the ionic stannate and germanate compounds display a higher anticancer activity and a degree of selectivity in vitro, compared to the neutral species. Concurrent research has focused on heterobimetallic systems (Chart 1).…”

Section: Introductionmentioning

confidence: 99%