Synthesis, physicochemical characterization and antiproliferative activity of phosphino Ru(ii) and Ir(iii) complexes. Issue 22 (26th May 2022)

• Record Type: Journal Article
• Authors: Komarnicka, Urszula K.; Kozieł, Sandra; Skórska-Stania, Agnieszka; Kyzioł, Agnieszka; Tisato, Francesco
• Is Part Of: Dalton transactions. Volume 51:Issue 22(2022)
• Page Start: 8605
• Page End: 8617
• Publication Date: 2022-05-26
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d2dt01055k
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : We present the synthesis, physicochemical and biological activity of new Ru(ii ) and Ir(iii ) complexes ((Ru(η 6 - p -cymene)Cl2 PPh2 CH2 OH, Ru(η 6 - p -cymene)Cl2 P( p -OCH3 Ph)2 CH2 OH), (Ir(η 5 -Cp*)Cl2 P( p -OCH3 Ph)2 CH2 OH, Ir(η 5 -Cp*)Cl2 PPh2 CH2 OH). Abstract : Herein, we present the synthesis of new complexes based on ruthenium(ii ) (Ru(η 6 - p -cymene)Cl2 PPh2 CH2 OH (RuPOH ) and Ru(η 6 - p -cymene)Cl2 P( p -OCH3 Ph)2 CH2 OH (RuMPOH )) and iridium(iii ) (Ir(η 5 -Cp*)Cl2 P( p -OCH3 Ph)2 CH2 OH (IrMPOH ) and Ir(η 5 -Cp*)Cl2 PPh2 CH2 OH (IrPOH )) containing phosphine ligands with/without methoxy motifs on phenyl rings (P( p -OCH3 Ph)2 CH2 OH (MPOH ) and PPh2 CH2 OH (POH )). The complexes were characterized by mass spectrometry, NMR spectroscopy (1D: 1 H, 13 C{ 1 H}, and 31 P{ 1 H} and 2D: HMQC, HMBC, and COSY NMR) and elemental analysis. All the complexes were structurally identified by single-crystal X-ray diffraction analysis. The Ru(ii ) and Ir(iii ) complexes have a typical piano-stool geometry with an η 6 -coordinated arene (Ru II complexes) or η 5 -coordinated (Ir III compounds) and three additional sites of ligation occupied by two chloride ligands and the phosphine ligand. Oxidation of NADH to NAD + with high efficiency was catalyzed by complexes containing P( p -OCH3 Ph)2 CH2 OH (IrMPOH and RuMPOH ). The catalytic property might have important future applications in biological and medical fields like production of reactive oxygen species (ROS). Furthermore, the redox activity of the complexes was confirmed by cyclic voltamperometry. Biochemical assays demonstrated the ability of Ir(iii ) and Ru(ii ) complexes to induce significant cytotoxicity in various cancer cell lines. Furthermore, we found that RuPOH and RuMPOH selectively inhibit the proliferation of skin cancer cells (WM266-4; IC50, after 24 h: av. 48.3 μM; after 72 h: av. 10.2 μM) while Ir(iii ) complexes were found to be moderate against prostate cancer cells (DU145).