A binuclear Cu(II) complex as an efficient photocatalyst for N-alkylation of aromatic amines.

Visible-light driven photoreactions using transition metal complexes as catalysts are currently a research hotspot in developing environmentally friendly sustainable processes. To develop a potential copper-based photocatalyst, a binuclear Cu(II) complex has been synthesized using a Mannich base ligand viz. 2,4-dichloro-6-((4-(2-hydroxyethyl)piperazin-1-yl)methyl)phenol (H2L). The photocatalyst has been characterized using ESI-MS and single crystal X-ray diffraction. Under the irradiation of visible light, the catalyst can catalyze hydrogen auto-transfer in N-alkylated amine formation and benzyl alcohol oxidation reactions with excellent conversion. A plausible mechanistic pathway for catalytic reactions has been explored through ESI-MS spectrometric, UV-Vis spectroscopic and computational studies.

Mechanistic Insight for Targeting Biomolecules by Ruthenium(II) NSAID Complexes.

With the enormous progress in ruthenium complexes as promising anticancer agents after the entry of KP1019, KP1339, and NAMI-A in clinical trials, herein three arene ruthenium(II) NSAID (nonsteroidal anti-inflammatory drugs) complexes viz. [Ru(η6-p-cymene)(mef)Cl] (1), [Ru(η6-p-cymene)(flu)Cl] (2), and [Ru(η6-p-cymene)(dif)Cl] (3) are synthesized, characterized, and reported. Density functional theory (DFT) calculations were performed in support of the obtained experimental results by computing the equilibrium geometries, reactions pathways, relative Gibbs free energy, stability, and reactions barriers of the complexes. The present theoretical study shows that all the proposed structures of the complexes are energetically stable and favorable, and the results obtained are in close accordance with the experiment. Further, the in vitro cytotoxicity of the complexes was explored through MTT assay on MCF-7, Hela, A549, and HEK cell lines. It was found the complex 1 and 2 are significantly cytotoxic toward the MCF-7 cell line. These complexes have also shown a strong affinity toward CT-DNA and proteins (HSA and BSA) as analyzed through spectroscopic techniques. Further investigation of the mechanism of cell death of selected complexes was carried out by various staining, flow cytometry, and gene expression analysis obtained by RT-PCR.

Mannich base Cu(II) complexes as biomimetic oxidative catalyst.

Galactose Oxidase (GOase) and catechol oxidase (COase) are the metalloenzymes of copper having monomeric and dimeric sites of coordination, respectively. This paper summarizes the results of our studies on the structural, spectral and catalytic properties of new mononuclear copper (II) complexes [CuL(OAc)] (1), and [CuL2] (2), (HL = 2,4­dichloro­6­{[(2'­dimethyl­aminoethyl)methylamino]methyl}­phenol) which can mimic the functionalities of the metalloenzymes GOase and COase. The structure of the compounds has been elucidated by X-ray crystallography and the mimicked Cu(II) catalysts were further characterized by EPR. These mimicked models were used for GOase and COase catalysis. The GOase catalytic results were identified by GC-MS and, analyzed by HPLC at room temperature. The conversion of benzyl alcohol to benzaldehyde were significant in presence of a strong base, Bu4NOMe in comparison to the neutral medium. Apart from that, despite of being monomeric in nature, both the homogeneous catalysts are very prone to participate in COase mimicking oxidation reaction. Nevertheless, during COase catalysis, complex 1 was found to convert 3,5­ditertarybutyl catechol (3,5-DTBC) to 3,5­ditertarybutyl quinone (3,5-DTBQ) having greater rate constant, kcat or turn over number (TON) value over complex 2. The generation of reactive intermediates during COase catalysis were accounted by electrospray ionization mass spectrometry (ESI-MS). Through mechanistic approach, we found that H2O2 is the byproduct for both the GOase and COase catalysis, thus, confirming the generation of reactive oxygen species during catalysis. Notably, complex 1 having mono-ligand coordinating atmosphere has superior catalytic activity for both cases in comparison to complex 2, that is having di-ligand environment.