Oxovanadium(IV) and ruthenium(II) carbonyl complexes of ONS‐donor ligands derived from dehydroacetic acid and dithiocarbazate: Synthesis, characterization, antioxidant activity, DNA binding and in vitro cytotoxicity

Abstract

A series of new complexes of oxovanadium(IV) [VO(L)(B)] and ruthenium(II) [Ru(CO)(PPh3)2(L)] (1.1- 1.3, 2.1–2.3) (H2L = dehydroacetic acid Schiff base of S‐methyldithiocarbazate, H2smdha (1) or S‐benzyldithiocarbazate, H2sbdha (2); B = 2,2′‐bipyridine (bpy) or 1,10‐phenanthroline (phen)) have been synthesized. The structure of these complexes was authenticated using elemental analyses and spectroscopic techniques, and their magnetic properties and electrochemical behaviour were studied. The molecular structures of oxovanadium(IV) complexes [VO(smdha)(bpy)]⋅CH2Cl2 (1.1) and [VO(sbdha)(phen)]⋅2H2O (2.2) were confirmed using single‐crystal X‐ray crystallography. Analytical data showed that the ligands 1 and 2 are chelated to the metal centres in a bi‐negative tridentate fashion through azomethine N, thiol S and deprotonated hydroxyl group. The antioxidant activity of the synthesized compounds was tested against 2,2‐diphenyl‐1‐picrylhydrazyl) radical, which showed that the complexes demonstrate a better scavenging activity than their corresponding ligands. The cupric ion reducing antioxidant capacity method was also employed and the total equivalent antioxidant capacity values were found to be higher for the oxovandium(IV) complexes. DNA binding affinity of the compounds was determined using UV–visible and fluorescence spectra, revealing an intercalation binding mode. Higher cytotoxicity for the complexes compared to their ligands was found against human liver hepatocellular carcinoma (HepG2) and breast adenocarcinoma (MCF7) cell lines using MTT assay.

Synthesis, characterization, DNA binding/cleavage, cytotoxic, apoptotic, and antibacterial activities of V(IV), Mo(VI), and Ru(II) complexes containing a bioactive ONS‐donor chelating agent

“…[21,53] Also, the band due to thione ν(C S) disappeared followed by appearance of new bands in 717-767 cm −1 region due to formation of thiolate group ν(C-S). [20,21,29,54] This concludes that the ligand is coordinated to the metal center through azomethine nitrogen, deprotonated phenolate oxygen, and thiolate sulfur in a bi-negative tridentate manner. [20,29,43] The thione-thiole forms of the ligand are indicated in Scheme 1.…”

“…Reddish-brown product, yield 81%; mp 250 C (decomp. ); elemental analyses for C 20 [MoO 2 (dhasm)(B)] (B = imz (3) or DMSO (4)) The ligand H 2 dhasm (0.123 g, 0.5 mmol) in methanol was added to a solution of [MoO 2 (acac) 2 ] (0.163 g, 0.5 mmol) in methanol (10 ml). After 15 min of stirring at room temperature, an orange solution was obtained, then an imidazole (0.04 g, 0.5 mmol) or DMSO (400 μl, 0.5 mmol) was added.…”

“…It affords new chemical features for the complexes concerning their structure, electronic and biological applications. [19] Continuing to our work, [20,21] we herein have synthesized a series of new metal complexes of V(IV), Mo(VI), and Ru(II) with Schiff base derived from 2,4-dihydroxyacetophenone and S-methyldithiocarbazate (H 2 dhasm). The ligand and complexes were spectroscopically characterized and X-ray crystal structure of the complexes cis-[MoO 2 (dhasm((B)] (B = imz (3), B = DMSO (4)) was determined.…”

Modification of insulin amyloid aggregation by Zr phthalocyanines functionalized with dehydroacetic acid derivatives

“…Dehydroacetic acid (DHA) is the basic material for the synthesis of a very wide range of organic compounds, in particular β-ketoenoles, described in many reviews [18][19][20]. DHA derivatives were studied for their antioxidant and cytotoxic [21], antitumor [22], antimicrobial [23][24][25] and other properties. The interaction of DHA with aromatic aldehydes leads to the formation of halcones [26,27], which serve as starting compounds to obtain alkylamino-βketoenoles.…”

Thiosemicarbazone Complexes of Transition Metals as Catalysts for Cross-Coupling Reactions

“…Thiosemicarbazone metal complexes have also found potential application in medical imaging [27,28], while thiosemicarbazones themselves show promise as metal ion sensors and for the scavenging of metals due to their selective and specific coordination properties [28][29][30][31][32][33][34]. Although related compounds such as isothiosemicarbazones, dithiocarbazates, and selenosemicarbazones have so far found less application in the catalysis of coupling reactions and will not feature in this review, it is appropriate to mention that a number of metal complexes have nevertheless been reported and that they too have been studied in areas such as oxidation processes [35][36][37], cytotoxicity [38][39][40][41][42][43][44][45][46][47], antimicrobials [48], imaging [49,50], and antioxidants [43,51,52].…”