Rhodium‐catalysed hydroformylation of 1‐octene using aryl and ferrocenyl Schiff base‐derived ligands

Monometallic and heterobimetallic complexes of Rh(I) bearing chelating N ,O ‐bidentate aryl‐ and ferrocenyl‐derived ligands have been synthesised via Schiff base condensation reactions, and characterised fully using ¹H NMR, ¹³C{¹H} NMR and Fourier transform infrared spectroscopies, elemental analysis and mass spectrometry. The new monometallic and heterobimetallic complexes were evaluated as potential catalyst precursors in the hydroformylation of 1‐octene at 95°C and 40 bar. The ferrocenylimine mononuclear compounds were inactive in the hydroformylation experiments. The Rh(I) monometallic and the ferrocene–Rh(I) heterobimetallic pre‐catalysts displayed good activity and conversion of 1‐octene as well as outstanding chemoselectivity towards aldehydes in the hydroformylation reaction.     

Novel coordination polymers with ferrocene-containing dicarboxylate ligand: Syntheses, crystal structures and properties

A new ferrocene-containing dicarboxylate ligand, L = 5-ferrocene-1,3-benzenedicarboxylic acid, has been prepared. Self-assembly of L, M(II) salts (M = Co and Zn) and chelating ligands dpa or phen (dpa = 2,2′-dipyridylamine and phen = 1,10-phen) gave rise to four new coordination polymers {[Co(L)(dpa)] · 2MeOH}_n (1), {[Zn(L)(dpa)] · 2MeOH}_n (2), {[Co(L)(phen)(H₂O)] · MeOH} (3), [Zn(L)(phen)(H₂O)] · MeOH (4). The isostructural complexes 1 and 2 possess 1D helical chain structures with 2₁ screw axes along the b-direction, and the right- and left-handed helical chains are alternate arrayed into 2D layer structures through hydrogen-bonding interactions; while isostructural complexes 3 and 4 are 1D linear chain structures with phen and ferrocene groups of L as pendants hanging on the different sides of the main chain. A structural comparison of complexes 1–4 demonstrated that the characteristics of subsidiary ligands and slight difference in coordination models of L play very important role in the construction of the complexes. In addition, the redox properties of complexes 1–4, as well as the magnetic properties of complexes 1 and 3 are also investigated.     

Ferrocene conjugated copper(II) complexes of terpyridine and traditional Chinese medicine (TCM) anticancer ligands showing selective toxicity towards cancer cells

Six novel mixed‐ligand copper(II) complexes, namely, [Cu(R‐tpy)(L)]NO₃ ( 1–6 ), where R‐tpy is 4′‐phenyl‐2,2′:6′,2′′‐terpyridine (Ph‐tpy; 1–3 ) and 4′‐ferrocenyl‐2,2′:6′,2′′‐terpyridine (Fc‐tpy; 4–6 ), L is the bidentate O,O donor monoanion of plumbagin (5‐hydroxy‐2‐methyl‐1,4‐naphthoquinone; plum in 1 , 4 ), chrysin (5,7‐dihydroxyflavone; chry in 2 , 5 ) and curcumin (bis(4‐hydroxy‐3‐methoxyphenyl)‐1,6‐diene‐3,5‐dione; curc in 3 , 6 ) have been synthesized and characterized and their in vitro cytotoxicity against cancer cells is evaluated. The energy optimized structures and the frontier orbitals of the complexes have been obtained from the DFT calculations. Complexes 4–6 with a conjugated ferrocenyl moiety and TCM anticancer ligands, namely, plum (in 4 ), chry (in 5 ) and curc (in 6 ) showed potent cytotoxicity giving respective IC₅₀ values of 1.2 μM, 0.62 μM and 0.21 μM in HeLa and 2.0 μM and 1.0 μM and 0.34 μM in MCF‐7 cancer cells while being much less toxic to MCF‐10A normal cells (IC₅₀: 8.3‐17.1 μM). In contrast, complexes 1–3 with a conjugated phenyl moiety were appreciably less toxic to HeLa cells with respective IC₅₀ values of 10.4 μM, 8.1 μM and 5.5 μM when compared with their ferrocenyl analogues 4–6 . Mechanistic studies using Hoechst staining and Annexin‐V‐FITC assays on cancer cells revealed an apoptotic pathway of cell death induced by the complexes. Fluorescence imaging study showed that complex 6 having curcumin as ligand localized primarily in the mitochondria of HeLa cells. Thus, we demonstrate in this study that ferrocene conjugation to copper(II) complexes of TCM anticancer ligands significantly increases the selectivity and cytotoxicity of the resulting complexes towards cancer cells over normal cells.     

Neutral and cationic half‐sandwich arene d6 metal complexes containing pyridyl and pyrimidyl thiourea ligands with interesting bonding modes: Synthesis,structural and anti‐cancer studies

The reaction of [(p‐cymene)RuCl₂]₂ and [Cp*MCl₂]₂ (M = Rh/Ir) with benzoyl (2‐pyrimidyl) thiourea (L1) and benzoyl (4‐picolyl) thiourea (L2) led to the formation of cationic complexes bearing formula [(arene) M (L1)к² _(N,S) Cl]⁺ and [(arene) M (L2)к²_(N,S)Cl]⁺ [(arene) = p‐cymene, M = Ru, ( 1 , 4 ); Cp*, M = Rh ( 2 , 5 ) and Ir ( 3 , 6 )]. Precursor compounds reacted with benzoyl (6‐picolyl) thiourea (L3) affording neutral complexes having formula [(arene) M (L3)к¹_(S)Cl₂] [arene = p‐cymene, M = Ru, ( 7 ); Cp*, M = Rh ( 8 ), Ir ( 9 )]. X‐ray studies revealed that the methyl substituent attached to the pyridine ring in ligands L2 and L3 affects its coordination mode. When methyl group is at the para position of the pyridine ring (L2), the ligand coordinated metal in a bidentate chelating N, S‐ mode whereas methyl group at ortho position (L3), it coordinated in a monodentate mode. Further the anti‐cancer studies of the thiourea derivatives and its complexes carried out against HCT‐116, HT‐29 (human colorectal cancer), Mia‐PaCa‐2 (human pancreatic cancer) and ARPE‐19 (non‐cancer retinal epithelium) cell lines showed that the thiourea ligands are inactive but upon complexation, the metal compounds displayed potent and selective activity against cancer cells in vitro. Iridium complexes were found to be more potent as compared to ruthenium and rhodium complexes.     

Half‐sandwich ruthenium,rhodium and iridium complexes featuring oxime ligands: Structural studies and preliminary investigation of in vitro and in vivo anti‐tumour activities

Half‐sandwich ruthenium, rhodium and iridium complexes ( 1 – 12 ) were synthesized with aldoxime ( L1 ), ketoxime ( L2 ) and amidoxime ( L3 ) ligands. Ligands have the general formula [PyC(R)NOH], where R = H ( L1 ), R = CH₃ ( L2 ) and R = NH₂ ( L3 ). Reaction of [{(arene)MCl₂}₂] (arene = p ‐cymene, benzene, Cp*; M = Ru, Rh, Ir) with ligands L1 – L3 in 1:2 metal precursor‐to‐ligand ratio yielded complexes such as [{(arene)MLκ²_(N∩N)Cl}]PF₆. All the ligands act as bidentate chelating nitrogen donors in κ²_(N∩N) fashion while forming complexes. In vitro anti‐tumour activity of complexes 2 and 10 against HT‐29 (human colorectal cancer), BE (human colorectal cancer) and MIA PaCa‐2 (human pancreatic cancer) cell lines and non‐cancer cell line ARPE‐19 (human retinal epithelial cells) revealed a comparable activity although complex 2 demonstrated greater selectivity for MIA PaCa‐2 cells than cisplatin. Further studies demonstrated that complexes 3 , 6 , 9 and 12 induced significant apoptosis in Dalton's ascites lymphoma (DL) cells. In vivo anti‐tumour activity of complex 2 on DL‐bearing mice revealed a statistically significant anti‐tumour activity (P  = 0.0052). Complexes 1 – 12 exhibit HOMO–LUMO energy gaps from 3.31 to 3.68 eV. Time‐dependent density functional theory calculations explain the nature of electronic transitions and were in good agreement with experiments.     

Non–symmetrically p–nitrobenzyl–substituted N–heterocyclic carbene–silver(I) complexes as metallopharmaceutical agents

In the present work, a series of eight new imidazole, 4,5–dichloroimidazole, 4,5–diphenylimidazole and benzimidazole based nitro–functionalized mono–N –heterocyclic carbene (NHC)–silver(I) acetate ( 7a–d ) and bis–NHC–silver(I) hexafluorophosphate complexes ( 8a–d ) were synthesised by the reaction of the corresponding azolium hexafluorophosphate salts ( 6a–d ) with silver(I) acetate and silver(I) oxide in methanol and acetonitrile, respectively. All the synthesised compounds were fully characterized by various spectroscopic techniques and elemental analyses. Additionally, the structure of bis–(1–benzyl–3–(p –nitrobenzyl)–4,5–dichloroimidazole–2–ylidene)silver(I) hexafluorophosphate complex ( 8b ) was confirmed by single crystal X–ray diffraction analysis. Preliminary in vitro antibacterial evaluation was conducted for all the compounds ( 6a–d) , ( 7a–d) , and ( 8a–d) by Kirby–Bauer's disc diffusion method followed by the determination of Minimum Inhibitory Concentration (MIC) from broth macrodilution method against five standard bacteria; two Gram–positive bacterial strains (Staphylococcus aureus and Bacillus subtilis) and three Gram–negative bacterial strains ( Escherichia coli , Shigella sonnei, and Salmonella typhi). All the hexafluorophosphate salts ( 6a – d) were found inactive against the tested bacterial strains and their corresponding mono– and bis–NHC–silver(I) complexes ( 7a–d and 8a–d ) exhibited moderate to high antibacterial activity with MIC value in the range 8–128 μg/mL. In addition, preliminary in vitro anticancer potential of all the silver(I) complexes ( 7a–d and 8a–d ) was determined against the human derived breast adenocarcinoma cells (MCF 7) by MTT assay. All the mono– and bis–NHC–silver(I) complexes ( 7a–d and 8a–d ) orchestrated high anticancer potential with IC₅₀ values ranging from 10.39 to 59.56 nM. In comparison, mono– NHC–silver(I) complexes performed better than the bis–NHC–silver(I) complexes.     

Carbonylrhodium complexes of pyridine ligands and their catalytic activity towards carbonylation of methanol

The cis‐[Rh(CO)₂ClL] (1) complexes, where L = 2‐methylpyridine (a), 3‐methylpyridine (b), 4‐methylpyridine (c), 2‐phenylpyridine (d), 3‐phenylpyridine (e), 4‐phenylpyridine (f), undergo oxidative addition reactions with various electrophiles, like CH₃I, C₂H₅I, C₆H₅CH₂Cl or I₂, to yield complexes of the types [Rh(CO)(COR)ClXL] (2) (where R = CH₃ (i), C₂H₅ (ii), X = I; R = C₆H₅CH₂ (iii), X = Cl) or [Rh(CO)ClI₂L] (3) and [Rh(CO)₂ClI₂L] (4). The pseudo‐first‐order rate constants of CH₃I addition with complexes 1 containing pyridine (g) and 2‐substituted pyridine (a and d) ligands were found to follow the order pyridine >2‐methylpyridine >2‐phenylpyridine. The catalytic activity of complexes 1 containing different pyridine ligands (a–g) on carbonylation of methanol was studied and, in general, a higher turnover number was obtained compared with that of the well‐known species [Rh(CO)₂I₂]^?. Copyright © 2002 John Wiley & Sons, Ltd.     

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

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.     

Syntheses and mesomorphic properties of new oxygen-bridged dicopper complex homologous derived from azo-containing salicylaldimine Schiff base ligands

The synthesis, characterization and liquid crystal properties of a homologous series of new tridentate 5-((4-ⁿalkoxyphenyl) azo)-N-(3-ydroxypropyl) salicylaldimine ligands (alkoxy = octloxy, decyloxy, dodecyloxy and tetradecyloxy) and their dicopper(II) complexes are reported. These ligands were prepared by the condensation of the 5-((4-ⁿalkoxyphenyl)azo)salicylaldehydes homologous with 3-amino-1-propanol. The ligands and their dicopper complexes have been characterized by IR, ¹H NMR, mass spectroscopy and elemental analyzes. The liquid crystalline properties of the ligands and the related dicopper complexes were studied by differential scanning calorimetry (DSC) and by using a polarizing microscope equipped with a heating and cooling stage. None of the free ligands exhibit liquid crystalline behavior but all of the dicopper complexes demonstrate a smectic A mesophase.     

Dose‐, time‐and lipophilicity‐dependent silver(I)–N‐heterocyclic carbene complexes: Synthesis,characterization and interaction with plasmid and Aedes albopictus DNA

Four new Ag(I)–N‐heterocyclic carbene (NHC) complexes ( 5 – 8 ) bearing symmetrically substituted NHC ligands have been synthesized starting from the corresponding benzimidazolium bromide salts which are accessible in a single step from N ‐substituted benzimidazoles (N ‐alkyl and N ‐aryl) and subsequently reacted with the basic metal source Ag₂O in acetonitrile–methanol. These compounds were characterized using elemental analyses, ¹H NMR, ¹³C NMR, Fourier transform infrared and UV–visible spectroscopic techniques, and molar conductivity. Single‐crystal structural studies for complex 5 show that the Ag(I) centre has a perfectly linear C–Ag–C coordination, with quasi‐parallel pairs of aromatic benzimidazole planes. All the complexes interact with Aedes albopictus DNA via intercalation mode by a large hypochromicity of 22 and 27% and smaller hypochromicity of 16 and 19%. Furthermore, all complexes exhibit efficient DNA cleavage activity via a non‐oxidative mechanistic pathway. The DNase activities of the test compounds revealed a time‐ and concentration‐dependent activity pattern. The Ag(I)–NHC complexes showed considerably higher DNA cleavage activity compared to their respective benzimidazolium salts at a lower concentration. The DNA cleavage of these complexes changed from a moderate effect to a good one, corresponding to the increasing lipophilicity order of the complexes as 5  <  6  <  7  <  8 (1.02, 1.05, 1.78 and 2.06 for 5 – 8 , respectively). This order is further corroborated with the DNA binding study, but with the exception of complex 5 , which shows a better binding ability for DNA (K _b = 3.367 × 10⁶) than complexes 6 – 8 (6.982 × 10⁵, 8.376 × 10⁵ and 1.223 × 10⁶, respectively).     

Anticancer activity of multinuclear arene ruthenium complexes coordinated to dendritic polypyridyl scaffolds

The rational development of multinuclear arene ruthenium complexes (arene = p-cymene, hexamethylbenzene) from generation 1 (G¹) and generation 2 (G²) of 4-iminopyridyl based poly(propyleneimine) dendrimer scaffolds of the type, DAB-(NH₂)_n (n = 4 or 8, DAB = diaminobutane) has been accomplished in order to exploit the ‘enhanced permeability and retention’ (EPR) effect that allows large molecules to selectively enter cancer cells. Four compounds were synthesised, i.e. [{(p-cymene)RuCl₂}₄G¹] (1), [{(hexamethylbenzene)RuCl₂}₄G¹] (2), [{(p-cymene)RuCl₂}₈G²] (3), and [{(hexamethylbenzene)RuCl₂}₈G²] (4), by first reacting DAB-(NH₂)_n with 4-pyridinecarboxaldehyde and subsequently metallating the iminopyridyl dendrimers with [(p-cymene)RuCl₂]₂ or [(hexamethylbenzene)RuCl₂]₂. The related mononuclear complexes [(p-cymene)RuCl₂(L)] (5) and [(hexamethylbenzene)RuCl₂(L)] (6) were obtained in a similar manner from N-(pyridin-4-ylmethylene)propan-1-amine (L). The molecular structure of 5 has been determined by X-ray diffraction analysis and the in vitro anticancer activities of the mono-, tetra- and octanuclear complexes 1–6 studied on the A2780 human ovarian carcinoma cell line showing a close correlation between the size of the compound and cytotoxicity.     

Investigation of Raman,FT-IR,EPR spectra and antimicrobial activity of 2-(5-H/Me/Cl-1<Emphasis Type="BoldItalic">H</Emphasis>-benzimidazol-2-yl)-phenol ligands and their Fe(NO<Subscript>3</Subscript>)<Subscript>3</Subscript> complexes

2-(5-H/Me/Cl-1H-benzimidazol-2-yl)-phenol ligands form 1:1 electrolytes, 5-coordinate monometallic complexes with iron(III) nitrate. The geometry of the [Fe(L)(OH)(H₂O)₂](NO₃) complexes was derived from theoretical calculation in DGauss/DFT level (DZVP basis set) on CACHE. In all of the complexes the ligands are bidentate, via one imine nitrogen atom and phenolate oxygen atom. The coordination is completed with a hydroxide ion, and two water molecules, adopting a distorted square pyramidal geometry. The structures of the compounds were confirmed on the basis of elemental analysis, molar conductivity, magnetic moment, FT-Raman, FT-IR (mid-IR, far-IR), EPR and u.v.–vis. The antimicrobial activities of the free ligands, their hydrochloride salts, and the complexes were evaluated using the disk diffusion method in dimethyl sulfoxide (DMSO) as well as the minimal inhibitory concentration (MIC) dilution method, against nine bacteria and the results are compared with several known antibiotic agents. Antifungal activities were reported for Candida albicans, Kluyveromyces fragilis, Rhodotorula rubra, Debaryomyces hansenii, Hanseniaspora guilliermondii, and the results were referenced against nystatin, ketaconazole, and clotrimazole antifungal agents. In most cases, the compounds tested showed broad-spectrum (Gram⁺ & Gram⁻ bacteria) activities that were either more active or as potent as the references.     

New fac-tricarbonyl rhenium(I) semicarbazone complexes: synthesis,characterization, and biological evaluation

Expanding our previous work on salicylaldehyde semicarbazone metal complexes as prospective anti-trypanosomal agents, five new fac-Re^I(CO)₃-containing complexes with ligands of this semicarbazone series were synthesized and characterized. An atypical coordination mode of these potentially tridentate ligands through only the carbonylic oxygen and the azomethine nitrogen (the so-called N,O fashion) was demonstrated by IR spectroscopy and supported by theoretical calculations. Three of the compounds showed moderate in vitro anti-Trypanosoma cruzi activity and increased activity with respect to the corresponding free ligands. The brominated ligands, 5-bromo-2-hydroxybenzaldehyde semicarbazone (L2) and 5-bromo-2-hydroxy-3-methoxybenzaldehyde semicarbazone (L5), led to the most active rhenium(I) complexes. These compounds are among the few reported examples of rhenium complexes bearing in vitro activity against T. cruzi.     

Some divalent metal(II) complexes of salicylaldehyde‐derived Schiff bases: Synthesis,spectroscopic characterization,antimicrobial and in vitro anticancer studies

Mononuclear transition metal(II) complexes of the type M(L)₂?2H₂O (where M = Co, Ni, Cu, Zn) have been synthesized from uninegative Schiff base ligands (HL₁–HL₄) designed by condensation of 4‐fluorobenzylamine with 2‐hydroxy‐1‐naphthaldehyde/3,5‐dichlorosalicylaldehyde/3,5‐dibromosalicylaldehyde/3‐bromo‐5‐chlorosalicylaldehyde. The compounds were successfully characterized using spectroscopic and physiochemical methods together with elemental analysis. Spectroscopic elucidation indicates a monobasic bidentate nature of ligands coordinated via deprotonated phenolic oxygen and azomethine nitrogen atom which suggests an octahedral geometry around the central metal ions. The complexes and ligands were screened for their in vitro antimicrobial activity against bacterial and fungal strains, the zinc(II) complexes being more active against the tested microbial strains. Further, the metal complexes were found to be more active than the uncomplexed ligands due to chelation process and, moreover, the complexes were more active against fungal strains than bacterial strains. Cytotoxic activities of all compounds were evaluated towards human alveolar adenocarcinoma epithelial cell line (A549), human breast adenocarcinoma cell line (MCF7), human prostate cancer cell line (DU145) and one normal human lung cell line (MRC‐5) using MTT colorimetric assay with doxorubicin as a standard. The zinc complexes were most active against the cancer cell lines and also found to be less toxic against MRC‐5 normal cell line than standard doxorubicin.     

Co(II), Ni(II), Cu(II) and Zn(II) complexes of aminothiazole‐derived Schiff base ligands: Synthesis,characterization, antibacterial and cytotoxicity evaluation,bovine serum albumin binding and density functional theory studies

Transition metal complexes of type M(L)₂(H₂O)_x were synthesized, where L is deprotonated Schiff base 2,4‐dihalo‐6‐(substituted thiazol‐2‐ylimino)methylphenol derived from the condensation of aminothiazole or its derivatives with 2‐hydroxy‐3‐halobenzaldehyde and M = Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺ (x = 0 for Cu²⁺ and Zn²⁺; x = 2 for Co²⁺ and Ni²⁺). The synthesized Schiff bases and their metal complexes were thoroughly characterized using infrared, ¹H NMR, electronic and electron paramagnetic resonance spectroscopies, elemental analysis, molar conductance and magnetic susceptibility measurements, thermogravimetric analysis and scanning electron microscopy. The results reveal that the bidentate ligands form complexes having octahedral geometry around Co²⁺ and Ni²⁺ metal ions while the geometry around Cu²⁺ and Zn²⁺ metal ions is four‐coordinated. The geometries of newly synthesized Schiff bases and their metal complexes were fully optimized in Gaussian 09 using 6–31 + g(d,p) basis set. Fluorescence quenching data reveal that Zn(II) and Cu(II) complexes bind more strongly to bovine serum albumin in comparison to Co(II) and Ni(II) complexes. The ligands and their complexes were evaluated for in vitro antibacterial activity against Escherichia coli ATCC 25922 (Gram negative) and Staphylococcus aureus ATCC 29213 (Gram positive) and cytotoxicity against lever hepatocellular cell line HepG2.     

Thermal behavior of some vanadyl complexes with flavone derivatives as potential insulin-mimetic agents

Two new complexes having general formula VOL₂·nH₂O [(1) L: 5-hydroxyflavone, n = 1; (2) L: chrysin, n = 4] were synthesized and characterized. Based on IR and electronic data we concluded that studied flavones act as bidentate ligands in complexes with metallic ion coordinated in a square-pyramidal stereochemistry. The thermal analysis (TG, DTA) elucidated the composition and also the number and nature of the water molecules. The thermal behavior also indicated strong interactions between oxovanadium (IV) and these oxygen donor ligands.     

Green Synthesis of new Trizole Based Heterocyclic Amino Acids Ligands and their Transition Metal Complexes. Characterization,Kinetics, Antimicrobial and Docking Studies

Two novel amino acids imine ligands (H₂L₁ and H₂L₂) have been synthesized using green condensation reaction from 2‐[3‐Amino‐5‐(2‐hydroxy‐phenyl)‐5‐methyl‐1,5‐dihydro‐[1, 2, 4]triazol‐4‐yl]‐3‐(1H‐indol‐3‐yl)‐propionic acid with benzaldehyde/p‐flouro benzaldehyde (1:1 molar ratio) in the presence of lemon juice as a natural acidic catalyst in aqueous medium. Their transition metal complexes have been prepared in a molar ratio (1:1). Characterization of the ligands and complexes using elemental analysis, spectroscopic studies, ¹HNMR, ¹³CNMR, and thermal analysis has been reported. E*, ΔH*, ΔS* and ΔG* thermodynamic parameters, were calculated to throw more light on the nature of changes accompanying the thermal decomposition process of these complexes. The molar conductance measurement of metal complexes showed nonelectrolyte behavior. The metal complexes of the two ligands have tetrahedral geometry with a general molecular structure [M(H₂L)X_n], where [(M = Mn (II), Co (II), Cu (II) and Zn (II), X = Cl, n = 2]; M = VO (II), X = SO₄, n = 1] for H₂L₁. [M = Co (II), Cu (II), Zn (II)] for H₂L₂. Antibacterial activity of the complexes against (Bacillis subtilis, Micrococcus luteus, Escherichia coli), also antifungal activity against (Aspergillus niger, Candida Glabarta, Saccharomyces cerevisiae) have been screened. The results showed that all complexes have antimicrobial activity higher than free ligands. Molecular docking studies results showed that, all the synthesized compounds having minimum binding energy and have good affinity toward the active pocket, thus, they may be considered as good inhibitor of targeting PDB code: 1SC7 (Human DNA Topo‐isomerase I).     

Influence of dicarboxylic acids on self-assembly process: Syntheses and structural characterization of new Ag(I) complexes derived from mixed ligands

Using the principle of crystal engineering, three new silver metal–organic coordination polymers, [Ag₂(L1)₂(L2)]·2H₂O (1), [Ag₂(L1)₂(L3)]·H₂O (2), [Ag₂(L1)₂(L4)]·2H₂O (3) (L1 = 2-aminopyrimidine, L2 = oxalate anion, L3 = glutarate anion and L4 = 1,4-naphthalenedicarboxylate anion) have been synthesized by solution phase reactions of silver nitrate with various dicarboxylic acids and cooperative heterocyclic 2-aminopyrimidine ligand under the ammoniacal conditions. All the complexes have been characterized by elemental analyses, IR spectra and X-ray diffraction. In complex 1, L1 ligands are coordinated to Ag(I) metal centers in rare tridentate fashions, forming one-dimensional (1-D) ladder-like structure, which is interlinked by L2 anions to generate 2-D pleated molecular sheet. Complex 2 displays an interesting two-dimensional (2-D) tongue-and-groove structure containing a new kind of “T-shaped” unit. Meanwhile, each of 2-D bilayers is interlocked by four adjacent identical motifs to form three-dimensional (3-D) 5-fold interpenetrating conformation with weak Ag···Ag interactions. In complex 3, L1 ligands are coordinated to the Ag(I) ions to form 1-D polymeric chain. And L4 anions, acting as bridging linkers through corresponding μ²-carboxylates, link a pair of Ag(I) atoms from adjacent chains to yield 3-D supramolecular network. The structures of complexes 1–3 which span from 2-D to 3-D networks suggest that dicarboxylate anions play important role in the formation of such coordination architectures.     

Cobalt complexes based on hyperbranched salicylaldimine ligands as catalyst precursors for ethylene oligomerization

Three hyperbranched salicylaldimine ligands with tetradecyl as core, with hexadecyl as core and with octadecyl as core were synthesized in good yields. These ligands were reacted with cobalt chloride hexahydrate to form three complexes ( C1 – C3 ). The compounds were characterized using Fourier transform infrared, ¹H NMR, mass and UV spectroscopies and thermogravimetric and differential thermal analyses. The catalytic properties of the hyperbranched cobalt complexes were evaluated for ethylene oligomerization. The effects of solvent and reaction parameters (Al/Co molar ratio, temperature and reaction pressure) on ethylene oligomerization were studied using the cobalt complex C3 as pre‐catalyst and methylaluminoxane (MAO) as co‐catalyst. Under these conditions ([Co] = 5 μmol, Al/Co = 500, 25 °C, 0.5 MPa ethylene, 30 min), the catalytic activity of complex C3 in toluene was 1.85 × 10⁵ g (mol Co)⁻¹ h⁻¹ and the selectivity for C₈₊ oligomers was 55.72%. The complex structure also had a significant influence on both the catalytic activity and selectivity. All three cobalt complexes, activated with MAO, showed moderate activities towards ethylene oligomerization and the activity of cobalt complex C1 was up to 1.99 × 10⁵ g (mol Co)⁻¹ h⁻¹. The kinds of metal center of complexes (cobalt complex C1 and nickel complex with tetradecyl as core) and their catalytic properties were investigated in detail under the same conditions.     

Synthesis, spectroscopic and theoretical studies of two novel tripodal imine-phenol ligands and their complexation with Fe(III)

Two novel tripodal imine-phenol ligands, cis,cis-1,3,5-tris{(2-hydroxybenzilidene)aminomethyl}cyclohexane (TMACHSAL, L¹) and of cis,cis-1,3,5-tris{[(2-hydroxyphenyl)ethylidene]aminomethyl}cyclohexane (Me₃-TMACHSAL, L²) have been synthesized and characterized by elemental analyses and various spectral (UV–vis, IR and ¹H and ¹³C NMR) data. The complexation reactions of the ligands with H⁺ and Fe(III) were investigated by potentiometric and spectrophotometric methods at an ionic strength of 0.1 M KCl and 25 ± 1 °C in aqueous medium. Three protonation constants each for ligands L¹ and L² were determined and were used as input data to evaluate the formation constants of the metal complexes. Formations of metal complexes of the types FeLH₃, FeLH₂, FeLH, FeL and FeLH₋₁ were depicted in solution. Experimental evidences suggested for a formation of tris(iminophenolate) type metal complex by the ligands. The ligand L¹ showed higher affinity towards iron(III) than L². The pFe value related to L¹ (pFe = 20.14) is approximately four units higher than L² (pFe = 16.41) at pH = 7.4. The structures of the metal complexes were proposed through the molecular mechanics calculation using MM3 force field followed by semi-empirical PM3 method.