Biological assays, electrochemical behavior, and theoretical DFT calculations of Ru(II) complexes of chiral phosphinite based based on β-amino alcohols: Transfer hyrogenation of ketones using a HCOOH/Et3N mixture

• Published in: Journal of molecular structure 2024-05, Vol.1303, p.137556, Article 137556
• Main Authors: Rafikova, Khadichakhan, Meriç, Nermin, Binbay, Nil Ertekin, Okumuş, Veysi, Sever, M. Şerif, Belyankova, Yelizaveta, Tursynbek, Saniya, Dauletbakov, Anuar, Sarah, Bayazit, Zolotareva, Darya, Yerassyl, Kamshyger, Dündar, Abdurahman, Güzel, Remziye, Aydemir, Murat
• Format: Article
• Language: English
• Subjects: Asymmetric transfer hydrogenation (ATH); Biological assay; CA and OCPA; DFT and CAM-B3LYP; Electrochemical properties; Β-amino alcohols
• ISSN: 0022-2860; 1872-8014
• DOI: 10.1016/j.molstruc.2024.137556

•The ruthenium complexes were studied theoretically using DFT/CAM-B3LYP level.•Hardness and HOMO-LUMO gap of the complexes including benzene fragment were lower.•The complexes had antioxidant, antimicrobial and DNA binding activities.•The ruthenium-based variants have different redox potentials.•Complex 8 was used in ATH in the presence of HCOOH-Et3N mixture as reducing agent. Synthesis of two phosphinite ligands based on β-amino alcohols, in high yields has been demonstrated. When we treated [Ru(arene)(μ-Cl)Cl]2 {arene:p-cymene,benzene} with chelating phosphinite ligands, we obtained neutral Ru(II)-complexes possessing the general formula [Ru(arene)phosphiniteCl2]. The structure of the ligands and complexes was confirmed using analytical and spectroscopic techniques. The quantum chemical calculations were carried out for the ruthenium complexes at the DFT/CAM-B3LYP level of theory in gas phase. The phosphinite complexes were subjected to cyclic voltammetry studies in order to determine the energies of HOMO and LUMO levels and to estimate their electrochemical and some electronic properties. Organic complex-based memory substrates were immobilized using TiO2-modified ITO electrodes, and the memory functions of phosphinite-based organic complexes were verified by chronoamperometry (CA) and open-circuit potential amperometry (OCPA). In the present study, the antioxidant potentials of ruthenium-based p-cymene and benzene complexes through DPPH radical scavenging, metal chelating, and reducing power activities were also determined. In addition, DNA binding abilities and antimicrobial activities of these complexes against pathogenic bacteria were studied. Finally, the ruthenium complex, (2S)-1-{[(2S)-2-[(diphenylphosphanyl)oxy]propyl][(1R)-1-phenylethyl]amino}propan-2-yldiphenyl phosphinitobis[dichloro(η6-benzene)ruthenium(II)] also catalyzed asymmetric transfer hydrogenation of acetophenone with high conversion (up to 99%) and good enantioselectivity (ee up to 89 %), in the existence of formic acid and triethylamine in dichloromethane medium under air atmosphere. Treatment of [Ru(arene)(μ-Cl)Cl]2 {arene:p-cymene,benzene} with chelating phosphinite ligands afforded neutral Ru(II)-complexes possessing the general formula [Ru(arene)phosphiniteCl2]. The quantum chemical calculations were carried out for the ruthenium complexes at the DFT/CAM-B3LYP level of theory in gas phase. The phosphinite complexes were subjected to cyclic voltammetry studies in order to deter