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Role of the (pseudo)halido ligand in ruthenium(II) p-cymene α-amino acid complexes in speciation, protein reactivity and cytotoxicity.
- Source :
- Dalton Transactions: An International Journal of Inorganic Chemistry; 11/21/2021, Vol. 50 Issue 43, p15760-15777, 18p
- Publication Year :
- 2021
-
Abstract
- The reactions of the dimeric complexes [RuX<subscript>2</subscript>(η<superscript>6</superscript>-p-cymene)]<subscript>2</subscript> (X = Br, I, SCN) with L -proline (ProH) and trans-4-hydroxy- L -proline (HypH), in methanol in the presence of NaOH, afforded [RuX(κ<superscript>2</superscript>N,O-Pro)(η<superscript>6</superscript>-p-cymene)] (X = Br, 1b; I, 1c; SCN, 1d) and [RuX(κ<superscript>2</superscript>N,O-Hyp)(η<superscript>6</superscript>-p-cymene)] (X = Br, 2b; I, 2c; SCN, 2d), respectively. Alternatively, the one-pot, sequential addition of the appropriate α-amino carboxylate and X<superscript>−</superscript> salt to [RuCl<subscript>2</subscript>(η<superscript>6</superscript>-p-cymene)]<subscript>2</subscript> led to [RuX(κ<superscript>2</superscript>N,O-Pro)(η<superscript>6</superscript>-p-cymene)] (X = N<subscript>3</subscript>, 1e; NO<subscript>2</subscript>, 1f; CN 1g) and [Ru(N<subscript>3</subscript>)(κ<superscript>2</superscript>N,O-Hyp)(η<superscript>6</superscript>-p-cymene)] (2e). Complexes [Ru(κ<superscript>3</superscript>N,O,O′-O<subscript>2</subscript>CCH(NH<subscript>2</subscript>)(R)O)(η<superscript>6</superscript>-p-cymene)] (R = CH<subscript>2</subscript>, 3h; R = CHMe, 4h; R = CH<subscript>2</subscript>CH<subscript>2</subscript>, 5h) were prepared from the reaction of [RuCl<subscript>2</subscript>(η<superscript>6</superscript>-p-cymene)]<subscript>2</subscript> with the appropriate α-amino acid and NaOH in refluxing isopropanol. Treatment of the L -serine (SerH<subscript>2</subscript>) derivative [RuCl(κ<superscript>2</superscript>N,O-SerH)(η<superscript>6</superscript>-p-cymene)] (3a) with 1,3,5-triaza-7-phosphaadamantane (PTA) in water at reflux produced [Ru(κ<superscript>2</superscript>N,O-Ser)(κP-PTA)(η<superscript>6</superscript>-p-cymene)]Cl ([3i]Cl). The products were isolated in good to excellent yields, and were characterized by elemental analysis, IR and multinuclear NMR spectroscopy. The structures of 1f and 2b–e were ascertained by X-ray diffraction studies. The behaviour of the complexes in water and cell culture medium was investigated by multinuclear NMR and UV-Vis spectroscopy, revealing a considerable influence of the monodentate ligand on the aqueous chemistry. Complexes 1d–e, 2d–e, 3h, 4h and [3i]Cl, showing substantial inertness in aqueous media, were assessed for their cytotoxicity towards A2780 and A2780cisR cancer cell lines and the noncancerous HEK 293T cell line. A selection of compounds was also investigated for Ru uptake in A2780 cells and interactions with cytochrome c as a model protein. Combined, these studies provide insights into the previously debated role of the 'leaving' ligand on the biological activity of Ru(II) arene α-amino acid complexes. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 14779226
- Volume :
- 50
- Issue :
- 43
- Database :
- Complementary Index
- Journal :
- Dalton Transactions: An International Journal of Inorganic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 154435424
- Full Text :
- https://doi.org/10.1039/d1dt03274g