Reactions of complexation of several tetraaza-macrocycles with Group 6 metal carbonyls.

Reactions of complexation of several tetraaza-macrocycles with Group 6 metal carbonyls.

Context in source publication

Context 1
... reactions of several tetraaza-macrocycles with Group 6 metal carbonyls form compounds ( Fig. 1) with a stoichiometry dependent on the size of the macrocycle and on the metal ...

Citations

... Macrocyclic complexes are more thermodynamically stable and more selective to metal ion chelates than open chains (Cheng et al, 2015). Many macrocyclic and macroacyclic metal complexes have been used as ion separation (Guerriero et al, 1995;Ilhan et al, 2007 andRuppert et al, 1988), in biological processes (Kong et al, 2000;Champness et al, 1994) asanti-tumor (Chaudhary et al, 2007 as anti-cancerous; (Tyagi et al, 2014) as environmental importance (Choi et al, 2001) in magnetic resonance imaging (MRI); (Buster et al, 1990;Goldstein et al, 1989) as photosensitizer; (Dolphin et al, 1994;Bonnett et al, 1995) as detecting tumor lesions; (Kosmas et al, 1992) as radiotherapeutic; (Cox et al, 1989;Blain et al, 1990) as RNA cleavage catalyst; (Amin et al, 1994;Buster et al, 1990) as NMR shift and relaxation agents; (Platzek et al, 1997;Kumar et al, 1999) as enzyme carriers in macrocyclic ligand environment; (Emara et al, 2006 andSaleh et al, 2005) as in biomedical sciences (Mewis et al, 2010;Costamagna et al, 2000). Recently few comprehensive reviews were also published on macrocyclic ligands and metal complexes and their applications have also appeared (Barefield et al, 2010;Srivastava et al, 2022;Korybut-Daszkiewicz et al, 2010;Rahul et al, 2021;Srivastava et al, 2022). ...
... Among all the hexacyanoferrates, of transition metals, nanoparticles of few metal transition series such as zinc, cobalt, chromium, iron, nickel and copper have significant attention of scientific fraternity due to their peculiar solid state represent in SEM analysis and structural attributes including chemical, photomagnetic, electro chromical, electro catalytical, ion exchanging and ion-sensing properties. Transition metals present in different oxidation states and can react with a various number of negatively charged ions (Costamagna et al., 2000). The activity of transition metals has started the development of novel metal-based drugs in medical system having various pharmacological applications and may introduced in unique therapeutic opportunities in medical field (Tao et al., 2010). ...
Article
Transition metal complexes of V(II) Cr (II), Zr (II), Ag (II) and Cd (II) were synthesized and characterized by X-ray diffraction analysis. Antimicrobial potential of these complexes with specified fungus and bacteria have been evaluated. Antibacterial screening of these complexes has been carried out against Escherichia coli, Salmonella typhi, Staphylococcus aureus, Bacillus cereus, Shigella flexneri, Pseudomonas aeruginosa and antifungal screening of these complexes have been carried out against Byssochlmys fulva, Aspergillus Niger, Aspergillus fumigatus. Silver ferrocyanide and Cadmium ferrocyanide have shown higher inhibitory effect against Staphylococcus aureus with 32mm and 30mm inhibition zone respectively. In antifungal activity also Silver ferrocyanide and Cadmium Ferrocyanide has shown maximum inhibition zone with 29mm and 25mm diameter respectively against Aspergillus Niger. Keywords: Transition metal complexes, antibacterial and anti-fungal activity
... Numerous macrocycles have as of late been explored which demonstrated fundamentally improved electrocatalytic activity towards oxygen reduction response (ORR) [2]. Other applications such as CO 2 -fixation catalysts [3], optical sensors for metal ions [4], metal ion-selective reagents [5], chromogenic ion-pair recognition of hydroxides [2], models for metalloenzyme active sites [6] and applications in biology and medicine [7] have been reported for this class of compounds. The photoisomerization ability has been observed for some of them [8]. ...
Article
Full-text available
In this work, a new macrocyclic cadmium complex, [Cd(ACE)I]2[CdI4] (1); ACE: 1,3,6,10,12,15-hexaazatricyclo[13.3.1.16,10]eicosane, was prepared by template method and characterized by elemental analysis, FT-IR spectroscopy and single-crystal X-ray diffraction. Structural analysis of the complex 1 revealed an ionic complex containing two cadmium atoms with tetrahedral (in anionic portion) and square-pyramidal (in cationic portion) geometries. Using the DFT calculations, thermodynamic stability of the first-row and group 12 metal complexes containing ACE ligand was investigated and then validated by comparing with the CSD analogues. Charge distribution pattern of ACE ligand was compared with cationic unit of 1 by NBO analysis to study of the charge variation of ligand after complexation. Graphical abstract
... Also, the functional groups of the pendant arms provide particular characteristics to the complexation as it has been observed in N-functionalizated polyazamacrocycles with increasing selectivity toward certain ions to provide thermodynamic stability. The most relevant polyazamacrocyclic ligands containing pendant substituents synthetized are from nine to 24 atoms with no extended p-delocalization, such as porphyrins, phthalocyanines, naphthalocyanines [1]. Recently, our research group synthetized tetraazamacrocycles bound with phenyl arms through amide linkages with high stability and the functionality of carbonyl oxygen and acidic NH hydrogen. ...
Article
s The recognition of histamine with copper and zinc complexes of polyazamacrocyclic ligans was studied. The molecular recognition of histamine from the metal complexes was determined by UV-Vis and ¹H NMR spectra in solution. In the coordination study of histamine with the Cu²⁺ complexes, different changes were observed in the charge transfer bands and in the d-d bands of the metal complexes. These observations indicate a change in the conformational geometry of the complexes and the formation of the adduct with histamine. According with the analysis by ¹H NMR, the chemical shifts of the H2 and H5 hydrogens of the histamine aromatic ring are caused by the interaction with Zn²⁺ complexes, the widening of the H2 signal suggests that the coordination occurs between the N3 of the imidazole ring of the histamine and the Zn²⁺ ion. These results showed the formation of histamine adducts with the Cu²⁺ and Zn²⁺ complexes, to give rise to a ternary complex.
... Due to the increasing applicability of azamacrocyclic compounds in biomimetic, catalytic, biology and medicine, these compounds have gained much consideration. They have found great significance in the arenas where metal complexes with exciting kinetic and thermodynamic stabilities toward metal release are necessary such as techniques like magnetic resonance imaging, imaging with radioisotopes and radiotherapy [142]. Aza-macrocyclic ligands are also dynamically used as antimicrobial agents and other biological properties [143][144][145][146]. ...
... Azamacrocyclic compounds received great attention due to the existence of donor nitrogen atoms and their applications in medicinal and modern chemical techniques such as imaging with radioisotopes, radiotherapy and magnetic resonance imaging, where metal complex with extreme kinetic and thermodynamic stability toward metal release is required [8]. ...
Article
Thermodynamic aspects of complexation process between 14-membered tetra-aza macrocycle ligand and four metal cations were studied in ethanol–water (EtOH–H2O) binary mixtures at different temperatures by applying conductometric method. In all the cases, the stability constants (logKf) of 1:1 formed complexes between ligand and cations were obtained by fitting the molar conductivity curves using the Genplot computer program and the formation constant values (logKf) were generally in the range of 1.41–2.70. The values of thermodynamic parameters, standard enthalpy and standard entropy were obtained from the temperature dependence of the stability constants using the Van’t Hoff plots. Complexes in every cases were found to be entropy stabilized, and the selectivity order of all the complexes changes as well as the changes in composition of the solvent mixtures. The experimental data was tested by using artificial neural network (ANN) technique and was in a good agreement with estimated data.
... Coordination chemistry allowed the design of thousands of compounds with macrocyclic ligand, of interest for the medical care and diagnosis, industrial catalysis, optics, electronics, solar energy harvesting or hydrometallurgical extraction [1][2][3]. Some of these compounds are species with saturated macrocycle [4][5][6]. ...
... The MIC (lg mL -1 ) values of the ligand and complexes (1)-(3) ...
Article
Full-text available
New species of type MLCl2·nH2O (M:Ni, n = 4.5; M:Cu, n = 0 and M:Zn, n = 0; L: (4,5-11,12)-bisphenylen-1,3,6,8,10,13-hexaazacyclotetradecan-bis(pyrid-3-yl)methanone resulted by 1,2-phenylendiamine, nicotinamide and formaldehyde template condensation) were synthesised. The complex features have been assigned from microanalytical, IR, UV–Vis, 1H NMR and EPR spectra as well as magnetic data at room temperature. Simultaneous TG/DTA and TG/DSC/EGA measurements were performed in order to evidence the thermal decomposition pattern and the nature of the gaseous products formed in each step. Processes as water and chloride elimination as well as fragmentation and oxidative degradation of the organic ligand were observed during the thermal decomposition. The final product of decomposition was metal(II) oxide. The obtained complexes exhibited an improved antimicrobial activity in comparison with the ligand, both on planktonic and biofilm embedded cells, as well as a low cytotoxicity. The microbicidal and anti-biofilm activity of the complex (3) against the Gram-negative strains recommend it for the development of new antimicrobial solutions for these emerging multidrug-resistant bacteria causing life-threatening infectious diseases often untreatable with the existing antimicrobial agents. The assay on HEp-2 cells indicates a low cytotoxicity for all complexes. The plethysmometry assays indicate an anti-inflammatory activity for Cu(II) complex.
... One interesting application in the field of coordination chemistry has been to investigate the use of Schiff-base ligands to develop phenoxo-bridged binuclear complexes with homometallic and/or heterometallic centres. Complexes based on Schiffbase ligands play important roles in biomedical [8,9], biomimetic, and catalytic systems [10,11] and in supporting liquid crystalline phases [12]. A number of Schiff-base complexes have been used as oxygen carriers to mimic complicated biological systems [7,11]. ...
Article
A new macrocyclic multidentate Schiff-base ligand Na4L consisting of two submacrocyclic units (10,21-bis-iminomethyl-3,6,14,17- tricyclo[17.3.1.18,12]tetracosa-1(23),2,6,8,10,12(24),13,17,19,21,-decaene-23,24-disodium) and its tetranuclear metal complexes with Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) are reported. Na4L was prepared via a template approach, which is based on the condensation reaction of sodium 2,4,6-triformyl phenolate with ethylenediamine in mole ratios of 2 : 3. The tetranuclear macrocyclic-based complexes were prepared from the reaction of the corresponding metal chloride with the ligand. The mode of bonding and overall geometry of the compounds were determined through physicochemical and spectroscopic methods. These studies revealed tetrahedral geometries about Mn, Co, and Zn atoms. However, square planar geometries have been suggested for NiII and CuII complexes. Biological activity of the ligand and its metal complexes against Gram positive bacterial strain Staphylococcus aureus and Gram negative bacteria Escherichia coli revealed that the metal complexes become more potentially resistive to the microbial activities as compared to the free ligand. However, thesemetal complexes do not exhibit any effects on the activity of Pseudomonas aeruginosa bacteria.There is therefore no inhibition zone.
... One interesting application in the field of coordination chemistry has been to investigate the use of Schiff-base ligands to develop phenoxo-bridged binuclear complexes with homometallic and/or heterometallic centres. Complexes based on Schiffbase ligands play important roles in biomedical [8,9], biomimetic, and catalytic systems [10,11] and in supporting liquid crystalline phases [12]. A number of Schiff-base complexes have been used as oxygen carriers to mimic complicated biological systems [7,11]. ...
Article
Full-text available
A new macrocyclic multidentate Schiff-base ligand Na4L consisting of two submacrocyclic units (10,21-bis-iminomethyl-3,6,14,17-tricyclo[17.3.1.1(8,12)]tetracosa-1(23),2,6,8,10,12(24),13,17,19,21,-decaene-23,24-disodium) and its tetranuclear metal complexes with Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) are reported. Na4L was prepared via a template approach, which is based on the condensation reaction of sodium 2,4,6-triformyl phenolate with ethylenediamine in mole ratios of 2 : 3. The tetranuclear macrocyclic-based complexes were prepared from the reaction of the corresponding metal chloride with the ligand. The mode of bonding and overall geometry of the compounds were determined through physicochemical and spectroscopic methods. These studies revealed tetrahedral geometries about Mn, Co, and Zn atoms. However, square planar geometries have been suggested for Ni(II) and Cu(II) complexes. Biological activity of the ligand and its metal complexes against Gram positive bacterial strain Staphylococcus aureus and Gram negative bacteria Escherichia coli revealed that the metal complexes become more potentially resistive to the microbial activities as compared to the free ligand. However, these metal complexes do not exhibit any effects on the activity of Pseudomonas aeruginosa bacteria. There is therefore no inhibition zone.
... As recently reviewed by Duncan and White [1], the unique redox and catalytic chemistry of Cu have justifi ed the development of an interface fi eld where novel Cu complexes have been identifi ed and their potential therapeutic uses in diff erent pathologies described. Metal complexes, including copper complexes with macrocyclic ligands, have been designed as chemical models of metalloenzymes [7,8,37]. Aza-macrocyclic ligands received considerable attention during the last decade due to their relationship to biomimetic and catalytic systems, since many coordination compounds with aza-macrocycles are electrocatalytically active in redox reactions [8,37]. ...
... Metal complexes, including copper complexes with macrocyclic ligands, have been designed as chemical models of metalloenzymes [7,8,37]. Aza-macrocyclic ligands received considerable attention during the last decade due to their relationship to biomimetic and catalytic systems, since many coordination compounds with aza-macrocycles are electrocatalytically active in redox reactions [8,37]. To be used as redox drugs, macrocyclic complexes with high kinetic and thermodynamic stabilities towards metal release are required. ...
... This is a required feature to avoid their dissociation in in vivo systems and, therefore, to prevent possible toxic eff ects and losses of activity. The N -functionalization of azamacrocycles may enhance their metal-ion selectivity and the stability of metal complexes depending on the coordination properties of the pendant arms [37]. ...
Article
The unique redox and catalytic chemistry of Cu has justified the development of novel Cu complexes for different therapeutic uses including cancer therapy. In this work, four pyridine-containing aza-macrocyclic copper(II) complexes were prepared (CuL1-CuL4) varying in ring size and/or substituents and their superoxide scavenging activity evaluated. CuL3, the most active superoxide scavenger, was further studied as a modulator of the cytotoxicity of oxaliplatin in epithelial breast MCF10A cells and in MCF7 breast cancer cells. Our results show that CuL3 enhances the therapeutic window of oxaliplatin, by both protecting non-tumour cells and increasing its cytotoxic effect in breast carcinoma cells. CuL3 is thus a promising complex to be further studied and to be used as a lead compound for the optimization of novel chemotherapy sensitizers.