Search Results (14)

The electrochemical oxidation of anodic metal (cobalt, nickel, zinc or cadmium) in a cell containing an acetonitrile solution of the ligand (E)-N-(2-(((2-hydroxynaphthalen-1-yl)methylene)amino)phenyl)-4-methylbenzenesulphonamide (H₂L) affords complexes with the general formula [ML] (M = Co, Ni, Zn and Cd). Additionally, it was possible to obtain complexes with the general formula [MLL′] when L′ = 2,2-bipyridine (2,2-bpy), 4,4-bipyridine (4-4′-bpy) or 1,10-phenanthroline (phen) was present in the electrolytic cell. All of the compounds obtained have been characterized via microanalysis, IR spectroscopy, mass spectrometry, UV–visible spectroscopy and, in the case of diamagnetic compounds, via ¹H NMR spectroscopy. Further structural and electronic characteristics of these adducts have been obtained via DFT simulations. The compounds NEt₄[CoL₂] (1), [NiL(H₂O)] (2), [NiL(CH₃CN)(H₂O)]₂ (3), [Ni₂L₂(4,4′-bpy)] (4), [Zn₂L₂(MeOH)₂] (5) and [ZnL(2,2′-bpy)](CH₃CN) (6) have been characterized via X-ray diffraction. In this paper, we present a detailed study of the different behavior of the above-mentioned ligand depending on the metal and/or the presence of ancillary ligands. Full article

In the field of green chemistry, the development of more sustainable and cost-efficient methods for synthesizing primary amines is of paramount importance, with catalyst research being central to this effort. This work presents a facile, aqueous-phase synthesis of highly active cobalt catalysts (Co-Ph@SiO₂(x)) via pyrolysis of silica-supported cobalt–phenanthroline complexes. The optimized Co-Ph@SiO₂(900) catalyst achieved exceptional performance (>99% conversion, >98% selectivity) in the reductive amination of acetophenone to 1-phenylethanamine using NH₃/H₂. Systematic studies revealed that its exceptional performance originates from the in situ pyrolysis of the cobalt–phyllosilicate complex. This process promotes the uniform distribution of metal cobalt nanoparticles, simultaneously enhancing porosity and imparting bifunctional (acidic and basic) properties to the catalyst, resulting in outstanding catalytic activity and selectivity. The catalyst demonstrated broad applicability, efficiently converting diverse ketones (aryl-alkyl, dialkyl, bioactive) and aldehydes (halogenated, heterocyclic, biomass-derived) into primary amines with high yields (up to 99%) and chemoselectivity (>40 examples). This sustainable, non-noble metal-based catalyst system offers significant potential for industrial primary amine synthesis and provides a versatile tool for developing highly selective and active heterogeneous catalysts. Full article

Polyphenolic compounds, such as flavonoids, possess important structural and physico-chemical characteristics that in combination with their biological properties render them an important class of natural compounds with medicinal prospects. Chrysin is a well-known flavone with antioxidant activity and a multitude of other beneficial properties. The potential of flavonoids to coordinate with metal ions leads to derivatives with enhanced biological profile. Within this framework, four novel heteroleptic complexes of cobalt and nickel with chrysin and the aromatic bidentate chelating agents 2,2′-bipyridine and 1,10-phenanthroline were synthesized, as well as physico-chemically and structurally characterized. The in vitro antioxidant efficiency of the synthesized complexes was examined via the 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay. All complexes showed notable radical scavenging capacity comparable to that of ascorbic acid, providing the incentive for further investigation of their therapeutic potential. Full article

The interaction of cobalt(II) with first-generation quinolones oxolinic acid (Hoxo), flumequine (Hflmq), pipemidic acid (Hppa) and cinoxacin (Hcx) in the presence of the N,N′-donor heterocyclic ligands 2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen) afforded a series of novel cobalt complexes, namely [Co(bipy)₂(oxo)](PF₆)₂·H₂O (1), [Co(phen)₂(oxo)](PF₆)₂·0.5CH₃OH·0.5H₂O (2), [Co(bipy)₂(flmq)](PF₆)₂·0.5CH₃OH·0.5H₂O (3), [Co(bipy)₂(ppa)](PF₆)₂·CH₃OH·0.5H₂O (4), [Co(phen)₂(cx)](PF₆)₂·CH₃OH·0.5H₂O (5), and [Co(phen)₂(flmq)](PF₆)·0.5CH₃OH·H₂O (6). The characterization of the complexes involved physicochemical techniques, various spectroscopies and single-crystal X-ray crystallography. The affinity of complexes to calf-thymus (CT) DNA was monitored with various techniques, suggesting intercalation in-between the DNA-nucleobases as the most probable interaction mode, which may be combined with electrostatic interactions as a result of the cationic nature of the complexes. The affinity of the complexes for bovine and human serum albumin proteins was monitored, and the determined corresponding albumin-binding constants revealed a tight and reversible interaction. Full article

We report the synthesis of novel cobalt complexes-based catalysts designed for the oscillatory Belousov–Zhabotinsky (BZ) reaction. For the first time, we introduce cobalt complex-based self-oscillating gels that demonstrate autonomous color oscillations within a BZ reagent solution, functioning without the need for any external stimuli. We created acrylamide-based self-oscillating gels containing immobilized tris(2,2′-bipyridine)cobalt(II) or tris(1,10-phenanthroline)cobalt(II) complexes and gels containing covalently bound (5-acrylamido-1,10-phenanthroline)bis(2,2′-bipyridine)cobalt(II), (5-acrylamido-1,10-phenanthroline)bis(1,10-phenanthroline) cobalt(II), or tris(5-acrylamido-1,10-phenanthroline)cobalt(II) complexes. When the BZ reaction takes place within the gels, it results in the observation of moving chemical waves and reversible color changes. We believe that Co-complexes-based self-oscillating gels have potential applications in the design of soft actuators and chemical devices for signal processing. Full article

Metal-containing compounds are an important class of chemotherapeutics used to treat various manifestations of cancer. Despite the widespread clinical use and success of metallopharmaceuticals, they are ineffective towards a sub-population of tumours called cancer stem cells (CSCs). CSCs evade current chemotherapeutic regimens (including metallopharmaceuticals) and promote cancer relapse and metastasis. Here, we report the synthesis, characterisation and anti-breast CSCs properties of a series of cobalt(III)-polypyridyl complexes with salicylic acid. The lead cobalt(III) complex 6 (containing 3,4,7,8-tetramethyl-1,10-phenanthroline) displayed low micromolar potency towards breast CSCs, significantly lower than the gold-standard anti-breast CSC agent, salinomycin, and the clinically used metallodrug, cisplatin. Mechanistic studies indicate that the cobalt(III) complex 6 induces its anti-breast CSC effect by entering breast CSCs, penetrating the nuclei, damaging nuclear DNA and triggering caspase-dependent apoptosis. The cytotoxic mechanism of action of the cobalt(III) complex 6 is also dependent on the modulation of cyclooxygenase-2 (COX-2) expression. This work highlights the anti-breast CSC properties of cobalt(III) coordination complexes with non-steroidal anti-inflammatory drugs (NSAIDs) and more widely spotlights the importance of metallopharmaceuticals in the development of new anticancer agents that can tackle chemotherapeutic-resistant sub-populations. Full article

In this work, we studied lead(II) and cobalt(II) complexation of derivatives [2-B₁₀H₉O(CH₂)₂O(CH₂)₂N₃]²⁻ and [2-B₁₀H₉O(CH₂)₅N₃]²⁻ of the closo-decaborate anion containing pendant azido groups in the presence of 1,10-phenanthroline and 2,2′-bipyridyl. Mononuclear [PbL₂{An}] and binuclear [Pb₂L₄(NO₃)₂{An}] lead complexes (where {An} is the N₃-substituted boron cluster) were isolated and studied by IR spectroscopy and elemental analysis. The mononuclear lead(II) complex [Pb(phen)₂[B₁₀H₉O(CH₂)₂O(CH₂)₂N₃] and the binuclear lead(II) complex [Pb₂(phen)₄(NO₃)₂[B₁₀H₉O(CH₂)₅)N₃] were determined by single-crystal X-ray diffraction. In complex [Pb₂(phen)₄(NO₃)₂[B₁₀H₉O(CH₂)₅)N₃], the boron cluster is coordinated by the metal atom only via the 3c2e MHB bonds. In complex [Pb(phen)₂[B₁₀H₉O(CH₂)₂O(CH₂)₂N₃], the coordination environment of the metal includes BH groups of the boron cluster and the oxygen atom of the exo-polyhedral substituent. When the reaction was performed in a CH₃CN/water mixture, the binuclear lead(II) complex [(Pb(bipy)NO₃)(Pb(bipy)₂NO₃)(B₁₀H₉O(CH₂)₂O(CH₂)₂N₃)]·CH₃CN·H₂O was isolated, where the boron cluster acts as a bridging ligand between lead atoms coordinated by the boron cage via the O atoms of the substituent and/or the BH groups. In the course of cobalt(II) complexation, the starting compound (Ph₄P)₂[B₁₀H₉O(CH₂)₅N₃] was isolated and its structure was also determined by X-ray diffraction. Although a number of lead(II) complexes with coordinated N₃ are known from the literature, no complexes with the boron cluster coordinated by the pendant N₃ group involved in the metal coordination have been isolated. Full article

Electronic absorption spectroscopy was used to study the ETR of surfactant–cobalt(III) complexes containing imidazo[4,5-f][1,10]phenanthroline, dipyrido[3,2-d:2′-3′-f]quinoxaline and dipyrido[3,2-a:2′,4′-c](6,7,8,9-tetrahydro)phenazine ligands by using ferrocyanide ions in unilamellar vesicles of dipalmitoylphosphotidylcholine (DPPC) and 1-butyl-3-methylimidazolium bromide ((BMIM)Br), at different temperatures under pseudo-first-order conditions using an excess of the reductant. The reactions were found to be second-order and the electron transfer is postulated as occurring in the outer sphere. The rate constant for the electron transfer reactions was found to increase with increasing concentrations of ionic liquids. Besides these, the effects of surfactant complex ions on liposome vesicles in these same reactions have also been studied on the basis of hydrophobicity. We observed that, below the phase transition temperature, there is an increasing amount of surfactant–cobalt(III) complexes expelled from the interior of the vesicle membrane through hydrophobic effects, while above the phase transition temperature, the surfactant–cobalt(III) complexes are expelled from the interior to the exterior surface of the vesicle. Kinetic data and activation parameters are interpreted in respect of an outer-sphere electron transfer mechanism. By assuming the existence of an outer-sphere mechanism, the results have been clarified based on the presence of hydrophobicity, and the size of the ligand increases from an ip to dpqc ligand and the reactants become oppositely charged. In all these media, the ΔS^# values are recognized as negative in their direction in all the concentrations of complexes employed, indicative of a more ordered structure of the transition state. This is compatible with a model in which these complexes and [Fe(CN)₆]⁴⁻ ions bind to the DPPC in the transition state. Thus, the results have been interpreted based on the self-aggregation, hydrophobicity, charge densities of the co-ligand and the reactants with opposite charges. Full article

Natural phospholipid (PL)_n extract from cultured green algae Dunaliela tertiolecta was used as the main component of cell membranes for studies on the interaction with trace metal Co(II). The phospholipids of the membranes were extracted from other biological components using TiO₂-µSPE cartridges selective for the phosphate group according to a completely new protocol. The interaction of Co(II) with natural and standard phospholipids, phosphatidylcholine (PC), phosphatidylethanolamine (PE), and phosphatidylglycerol (PG) are registered only in the presence of the additional chelating ligand 1,10-Phenathroline (Phen). 1,10-Phenathroline, as a model of humic substances in the marine environment, formed a neutral complex with Co(II) by the substitution of water molecules of central metal ions. The interaction of hydrophobic mixed-ligand complexes with phospholipids was enabled by the substitution of the remaining water molecules in the coordination shell of Co(II), which was registered by voltammetric measurements. The Co(II)-Phen-PL complex is reduced from the adsorbed state at −1.65 V by the transfer of two electrons, followed by its irreversible dissociation and desorption, indicating an EC mechanism. The interaction between the mixed-ligand complexes Co(II)-Phen-lipids was confirmed by atomic force microscopy (AFM). AFM images of PL, PL with Phen mixture and PL, Phen with Co(II) showed different 3D structures on the mica surface, indicating changes caused by the interaction between cobalt(II), 1,10-Phenanthroline and phospholipids. Full article

Cobalt hierarchical graphitic carbon nanoparticles (Co@HGC) (1), (2), and (3) were prepared by simple pyrolysis of a cobalt phenanthroline complex in the presence of anthracene at different temperatures and heating times, under a nitrogen atmosphere. The samples were used for the catalytic hydrogenation of 2,4-dinitrophenol. Samples (1) and (3) were prepared by heating at 600 °C and 800 °C respectively, while (2) was prepared by heating at 600 °C with an additional intermediate stage at 300 °C. This work revealed that graphitization was catalyzed by cobalt nanoparticles and occurred readily at temperatures of 600 °C and above. The nanocatalysts were characterized by Scanning Electron Microscopy SEM, energy dispersive X-ray analysis EDX, Raman, Xrd, and XPS. The analysis revealed the presence of cobalt and cobalt oxide species as well as graphitized carbon, while TEM analysis indicated that the nanocatalyst contains mainly cobalt nanoparticles of 3–20 nm in size embedded in a lighter graphitic web. Some bamboo-like multiwall carbon nanotubes and graphitic onion-like nanostructures were observed in (3). The structures and chemical properties of the three catalysts were correlated with their catalytic activities. The apparent rate constants k_app (min⁻¹) of the 2,4-dinitrophenol reductions were 0.34 for (2), 0.17 for (3), 0.04 for (1), 0.005 (no catalyst). Among the three studied catalysts, the highest rate constant was obtained for (2), while the highest conversion yield was achieved by (3). Our data show that an increase in agglomeration of the cobalt species reduces the catalytic activity, while an increase in pyrolysis temperature improves the conversion yield. The nanocatalyst enhances hydrogen generation in the presence of sodium borohydride and reduces 2,4-dinitrophenol to p-diamino phenol. The best nanocatalyst (3) was prepared at 800 °C. It consisted of uniformly distributed cobalt nanoparticles sheltered by hierarchical graphitic carbon. The nanocatalyst is easily separated and recycled from the reaction system and proved to be degradation resistant, to have robust stability, and high activity towards the reduction reaction of nitrophenols. Full article

Under moderate acidic conditions, the cationic (+3) complexes ions tris(1,10-phenanthroline)cobalt(III), [Co(phen)₃]³⁺, and hexamminecobalt(III), [Co(NH₃)₆]³⁺, efficiently promote the self-assembling process of the diacid 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (H₂TPPS₄) into J-aggregates. The growth kinetics have been analyzed according to a well-established autocatalytic model, in which the rate determining step is the initial formation of a nucleus containing m porphyrin units (in the range 2–3), followed by a stage whose rate constant k_c evolves as a power of time. The observed catalytic rate constants and the extent of J-aggregation increase on increasing the metal complex concentration, with the phen complex being the less active. The UV/Vis extinction spectra display quite broad envelops at the J-band, especially for the amino-complex, suggesting that electronic dipolar coupling between chromophores is operative in these species. The occurrence of spontaneous symmetry breaking has been revealed by circular dichroism and the measured dissymmetry g-factor decreases on increasing the aggregation rates. The role of these metal complexes on the growth and stabilization of porphyrin nano-assemblies is discussed in terms of the different degree of hydrophilicity and hydrogen bonding ability of the ligands present in the coordination sphere around the metal center. Full article

A novel photoactive complex was constructed from two non-photoactive ligands and cobalt (II) ions. Upon ultra violet (UV) irradiation (365 nm), the color of complex 1 changes from orange to violet. The ESR spectrum indicates that the photoactive phenomenon of complex 1 originates from an intermolecular energy transfer between the H₅DDCPBA ligand and phenanthroline ligand. This photoactive complex shows high thermal stability according to the investigation of thermogravimetric analyses. In addition, the temperature dependence of magnetic susceptibilities for the orange complex 1 was also investigated systematically. Full article

Cobalt pi-complexes, previously described in the literature and specially synthesized and characterized in this work, were used as catalysts in homogeneous oxidation of organic compounds with peroxides. These complexes contain pi-butadienyl and pi-cyclopentadienyl ligands: [(tetramethylcyclobutadiene)(benzene)cobalt] hexafluorophosphate, [(C₄Me₄)Co(C₆H₆)]PF₆ (1); diiodo(carbonyl)(pentamethylcyclopentadienyl)cobalt, Cp*Co(CO)I₂ (2); diiodo(carbonyl)(cyclopentadienyl)cobalt, CpCo(CO)I₂ (3); (tetramethylcyclobutadiene)(dicarbonyl)(iodo)cobalt, (C₄Me₄)Co(CO)₂I (4); [(tetramethylcyclobutadiene)(acetonitrile)(2,2′-bipyridyl)cobalt] hexafluorophosphate, [(C₄Me₄)Co(bipy)(MeCN)]PF₆ (5); bis[dicarbonyl(B-cyclohexylborole)]cobalt, [(C₄H₄BCy)Co(CO)₂]₂ (6); [(pentamethylcyclopentadienyl)(iodo)(1,10-phenanthroline)cobalt] hexafluorophosphate, [Cp*Co(phen)I]PF₆ (7); diiodo(cyclopentadienyl)cobalt, [CpCoI₂]₂ (8); [(cyclopentadienyl)(iodo)(2,2′-bipyridyl)cobalt] hexafluorophosphate, [CpCo(bipy)I]PF₆ (9); and [(pentamethylcyclopentadienyl)(iodo)(2,2′-bipyridyl)cobalt] hexafluorophosphate, [Cp*Co(bipy)I]PF₆ (10). Complexes 1 and 2 catalyze very efficient and stereoselective oxygenation of tertiary C–H bonds in isomeric dimethylcyclohexanes with MCBA: cyclohexanols are produced in 39 and 53% yields and with the trans/cis ratio (of isomers with mutual trans- or cis-configuration of two methyl groups) 0.05 and 0.06, respectively. Addition of nitric acid as co-catalyst dramatically enhances both the yield of oxygenates and stereoselectivity parameter. In contrast to compounds 1 and 2, complexes 9 and 10 turned out to be very poor catalysts (the yields of oxygenates in the reaction with cis-1,2-dimethylcyclohexane were only 5%–7% and trans/cis ratio 0.8 indicated that the oxidation is not stereoselective). The chromatograms of the reaction mixture obtained before and after reduction with PPh₃ are very similar, which testifies that alkyl hydroperoxides are not formed in this oxidation. It can be thus concluded that the interaction of the alkanes with MCPBA occurs without the formation of free radicals. The complexes catalyze oxidation of alcohols with tert-butylhydroperoxide (TBHP). For example, tert-BuOOH efficiently oxidizes 1-phenylethanol to acetophenone in 98% yield if compound 1 is used as a catalyst. Full article

Fluorescence spectroscopy and ultraviolet (UV) spectroscopy techniques coupled with cyclic voltammetry (CV) were used to study the interaction between salmon sperm DNA and 1,10-Phenanthroline cobalt(II) complex, [Co(phen)₂(Cl)(H₂O)]Cl·H₂O, where phen = 1,10-phenanthroline. The interaction between [Co(phen)₂(Cl)(H₂O)]⁺ and double-strand DNA (dsDNA) was identified to be intercalative mode. An electrochemical DNA biosensor was developed by covalent immobilization of probe single-strand DNA (ssDNA) related to human immunodeficiency virus (HIV) on the activated glassy carbon electrode (GCE). With [Co(phen)₂(Cl)(H₂O)]⁺ being the novel electrochemical hybridization indicator, the selectivity of ssDNA-modified electrode was investigated and selective detection of complementary ssDNA was achieved using differential pulse voltammetry (DPV). Full article