Synthesis and spectral studies of macrocyclic Pb(II), Zn(II), Cd(II) and La(III) complexes by template reaction of 1,2-bis(2-formylphenyl)ethane with metal nitrate and various diamine

Eight new macrocyclic complexes were synthesized by template reaction of 1,4-bis(3-aminopropoxy)butane or (±)-trans-1,2-diaminocyclohexane with metal nitrate and 1,2-bis(2-formylphenyl)ethane and their structures were proposed on the basis of elemental analysis, FT-IR, UV-Vis, molar conductivity measurements, ¹H NMR and mass spectra. The metals to ligand molar ratios of the complexes were found to be 1: 1. The complexes are 1: 2 electrolytes for Cd(II), Pb(II) and Zn(II) complexes and 1: 3 electrolytes for La(III) as shown by their molar conductivities (Λ_m) in DMSO at 10⁻³ mol L⁻¹. Due to the existence of free ions in these complexes, such complexes are electrically conductive. The configurations of Cd(II) and Zn(II) complexes were proposed to probably tetrahedral, La(III) complexes are octahedral and Pb(II) complexes are octahedral geometry in the L¹ complex and tetrahedral geometry in the L² complex.     

Fungicidal,bactericidal and antifertility activities of diorganosilicon(IV) complexes derived from benzothiazolines

Synthetic, structural and biological aspects of trigonal-bipyramidal, Me₂S(N—S)CI and octahedral, Me₂Si(N—S)₂ types of diorganosilicon(IV) complexes of heterocyclic benzothiazolines (N—SH) are described. The complexes were characterized by elemental analysis, molecular weight determination, conductance measurements and electronic, infrared, ¹H and ¹³C NMR spectroscopic studies. Some ligands and their corresponding dimethylsilicon(IV) complexes have been tested for their effects on several pathogenic fungi and bacteria and found to be quite active in this respect. Antifertility activity in male mice of some representative ligands and their silicon complexes was also evaluated and discussed.     

Cationic Gold(II) Complexes: Experimental and Theoretical Study**

Gold(II) complexes are rare, and their application to the catalysis of chemical transformations is underexplored. The reason is their easy oxidation or reduction to more stable gold(III) or gold(I) complexes, respectively. We explored the thermodynamics of the formation of [Au^II(L)(X)]⁺ complexes (L=ligand, X=halogen) from the corresponding gold(III) precursors and investigated their stability and spectral properties in the IR and visible range in the gas phase. The results show that the best ancillary ligands L for stabilizing gaseous [Au^II(L)(X)]⁺ complexes are bidentate and tridentate ligands with nitrogen donor atoms. The electronic structure and spectral properties of the investigated gold(II) complexes were correlated with quantum chemical calculations. The results show that the molecular and electronic structure of the gold(II) complexes as well as their spectroscopic properties are very similar to those of analogous stable copper(II) complexes.     

Green synthesis of new Ge(IV) complexes with bio-potent ligands and their antimicrobial,DNA cleavage,and antioxidant activities

Green microwave supported synthesis, spectral, antimicrobial, DNA cleavage, and antioxidant studies of Ge(IV) complexes with bio-potent ligands, 1-acetylferrocenehydrazinecarboxamide (L¹H) and 1-acetylferrocenehydrazinecarbothioamide (L²H) have been carried out. The ligands and their respective complexes have been characterized on the basis of elemental analysis, IR, ¹H and ¹³C NMR spectra, and X-ray powder diffraction studies. The ligands are coordinated to the Ge(IV) via azomethine nitrogen and thiolic sulfur atom/ enolic oxygen atom. Both ligands and their complexes demonstrated appreciable fungicidal and bactericidal properties. The metal complexes demonstrated stronger antimicrobial than the respective free ligands. DNA cleavage activity of the complexes study revealed higher activity of the complexes than the ligands. Antioxidant activity of the complexes was tested for their hydrogen peroxide scavenging.     

Complexation of 4-amino-1,3 dimethyl-2,6 pyrimidine-dione derivatives with cobalt(II) and nickel(II) ions: synthesis,spectral, thermal and antimicrobial studies

Four heterocyclic Schiff-base ligands derived from condensation of 4-amino-1,3 dimethyl-2,6 pyrimidine-dione with 2-hydroxybenzaldehyde, 2-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde and 4-(dimethylamino) benzaldehyde, (HL¹, L², HL³and L⁴), respectively, and their Co(II) and Ni(II) complexes have been prepared and characterized via elemental analysis, molar conductance, magnetic moment, thermal and XRPD analysis as well as spectral data (IR, ¹H-NMR, mass and solid reflectance). IR data reveal that the ligands are bidentate neutral ligands except HL¹, which is monobasic tridentate with coordination sites azomethine (N), carbonyl (O) and phenolic (O). Conductance data suggest that all complexes are non-electrolytes, except cobalt(II) complexes of L²and HL³are 1 : 1 electrolytes. The mass spectra confirm the proposed structure of the ligands and their complexes. The solid reflectance spectral data and magnetic moment measurements suggest octahedral, tetrahedral and square planar geometrical structures for the metal complexes. The spectral data were utilized to compute the important ligand field parameters B, β and Dq; LFSE also was calculated. The thermal behavior is also studied. Antibacterial and antifungal properties of the ligands and their complexes show broad-spectrum activities and the metal complexes show higher activity than the free ligands.     

Synthesis,characterization and antimicrobial activity of the Schiff bases derived from 2,4-disubstituted thiazoles and 3-methoxysalicylaldehyde,and their cobalt(II), copper(II), nickel(II) and zinc(II) complexes

Two new Schiff base ligands containing 2,4–disubstituted thiazoles and cyclobutane rings, 4-(1-methyl-1-phenylcyclobutane-3-yl)-2-(2-hydroxy-3-methoxybenzylidenehydrazino)thiazole (L¹H), 4-(1-methyl-1-p-xylylcyclobutane-3-yl)-2-(2-hydroxy-3-methoxybenzylidenehydrazino)thiazole (L²H) and their mononuclear complexes with a 1:2 metal–ligand ratio have been prepared from acetate salts of Co^II, Cu^II, Ni^II and Zn^II in EtOH. The authenticity of the ligands and their complexes have been established by microanalyses, i.r., ¹³C- and ¹H-n.m.r. spectra, and by magnetic susceptibility and conductivity measurements. The complexes are mononuclear. Thermal properties of the ligands and complexes have been studied by t.g.a. and d.s.c. techniques. Antimicrobial activities of the ligands and their complexes have been tested against six different microorganisms; three are yeast and three are bacteria. One of the ligands and many of the complexes were found to be active against some of the microorganisms studied.     

Antibacterial and Superoxide Dismutase Activity as Well as DNA Interactions of Ciprofloxacin‐Based Ternary Copper(II) Phenanthroline Complexes

. Five neutral mixed‐ligand mononuclear square‐pyramidal copper(II) complexes of the type [Cu(cpf)(Lⁿ)Cl] (cpf = ciprofloxacin and Lⁿ = phenanthroline derivatives) ( 1 – 5 ) were synthesized and characterized. The complexes were screened for their antibacterial activity and bactericidal activity against two Gram^(+ve) and three Gram^(–ve) microorganisms and the results showed that all complexes studied are more potent than the quinolone standard drug ciprofloxacin. Absorption titration, viscosity, and thermal denaturation measurement studies revealed that each of these square‐pyramidal complexes moderately interacts with calf thymus DNA. The binding constants for mixed ligand complexes are in order of 1.5 × 10⁴–3.0 × 10⁴ M^–1. Based on the data obtained in the DNA binding studies an intercalative mode of binding is suggested for these complexes. The nucleolytic cleavage activity of adducts and gyrase inhibition assay were studied on double stranded pUC19 DNA by gel electrophoresis experiments. From the SOD mimic study; the concentration of complexes ranging from 0.45 μM to 1.45 μM are enough to inhibit the reduction rate of NBT by 50 % (IC₅₀) in NADH/PMS system.     

Tuning the Excited State of Photoactive Building Blocks for Metal‐Templated Self‐Assembly

The reaction of 2,2′:4,4′′:4′,4′′′‐quaterpyridyl (qtpy), with d⁶ ruthenium(II) (Ru^II), and rhenium(I) (Re^I) metal centers has been investigated. The pendant pyridyl groups on the products have also been methylated to produce a second series of complexes containing coordinated Meqtpy²⁺. The absorption spectra of the complexes are dominated by intraligand and charge‐transfer bands. The ruthenium(II) complexes display broad unstructured luminescence consistent with emission from a Ru(d)→diimine(π*) manifold in acetonitrile solutions. In aqueous solutions, their emissions are weaker and the lifetimes are shorter. This effect is particularly acute for complexes incorporating coordinated dipyridylpyrazine, dppz, ligands. Although the emission of the ruthenium(II) complexes containing Meqtpy²⁺ is generally shorter than their qtpy analogs, it is notable that solvent‐dependent effects are much less intense. The rhenium(I) complexes also display broad unstructured luminescence but, compared with the ruthenium(II) systems, they have a relatively short lifetime in acetonitrile. Electrochemical studies reveal that all of the Ru^II complexes display chemically reversible metal‐based oxidations. Re^I complexes only display irreversible metal‐based oxidations. In most cases, the reduction processes were not fully chemically reversible. The electrochemical and optical studies reveal that the nature of the lowest excited state of these complexes—particularly, the systems incorporating dppz—is highly dependent on the nature of the coordinated ligands. Calculations indicate that, although the excited state of most of the complexes is centered on the qtpy or Meqtpy²⁺ ligands, the excited state of the complexes containing dppz ligands is switched away from the dppz by qtpy methylation. A crystallographic study on one of the dicationic ruthenium(II) structures reveals that it forms an inclusion complex with benzene.     

Synthesis,Characterization, DNA Binding Properties,and Antioxidant Activity of Novel Copper(II) and Zinc(II) Complexes with Bis(pyrrol‐2‐yl‐methylamine) Ligands

Three novel ligands H₄Lⁿ (n = 1–3) and their copper(II) and zinc(II) complexes were prepared and characterized on the basis of elemental analyses, molar conductivity, ¹H NMR, UV/Vis, and IR spectroscopy as well as mass spectrometry. DNA binding properties of the ligands and their complexes were investigated by absorption spectroscopy, ethidium bromide displacement experiments, and viscosity measurements. The experimental results indicate that the new ligands and their complexes can bind to DNA and the binding affinities of the complexes are higher than those of the ligands. In addition, the antioxidant activity of the ligands and complexes was determined by superoxide and hydroxyl radical scavenging methods in vitro, indicating that the complexes exhibit more effective antioxidant activity than the ligands alone.     

Synthesis,characterization and mass spectral studies on acrocyclic schiff base complexes of Pb(II), Zn(II) and La(III)

Six new macrocyclic complexes were synthesized by template reaction of (±)-1,4-bis(3-aminopropoxy)butane with metal(II) nitrate and 1,10-bis(2-formylphenyl)-1,4,7,10-tetraoxadecane or 1,7-bis(2-formylphenyl)-1,4,7-trioxaheptane and their structures were proposed on the basis of elemental analysis, FT-IR, UV-Vis, molar conductivity measurements, ¹H NMR and mass spectra. The metals to ligand molar ratios of the complexes were found to be 1: 1. The complexes are 1: 2 electrolytes for Pb(II) and Zn(II) complexes and 1: 3 electrolytes for La(III) as shown by their molar conductivities (Λ_m) in DMSO at 10⁻³ mol L⁻¹. Due to the existence of free ions in these complexes, such complexes are electrically conductive. The configurations of La(III) and Zn(II) complexes were proposed to probably octahedral.     

Spectral nature,antifungal activity and molecular structure of metal complexes of acetylpyrazine 4N-substituted thiosemicarbazones

Summary Nickel(II) and copper(II) complexes of acetylpyrazine 3-azabicyclo[3.2.2]-nonylthiosemicarbazone and nickel(II) complexes of acetylpyrazine ⁴N-methyl-, ⁴N-dimethyl-, and 3-hexamethyleneiminylthiosemicarbazone have been synthesized and characterized by their spectral and physical properties. Crystal structures for the nickel(II) complexes of the ⁴N-methyl- and ⁴N-dimethyl-derivatives, with a chloro ligand in the fourth coordination position, are included. The growth inhibition by the four thiosemicarbazones and their metal complexes against two human pathogenic fungi, Aspergillus niger and Paecilomyces variotii, have been evaluated.     

Spectroscopic Characterization and Biological Activity of Salicylaldehyde Thiazolyl Hydrazone Ligands and their Metal Complexes

Two novel bidentate Schiff base ligands, 2-(2-hydroxy-3,5-dichloro/diboromo) benzaldehyde-[4-(3-methyl-3-mesitylcyclobutyl)-1,3-thiazol-2-yl]hydrazone, L¹H, L²H and their transition metal complexes are reported. The new ligands and their complexes have been characterized by elemental analyses, Λ_M, infrared, u.v.–vis, ¹H- and ¹³C-n.m.r. spectroscopy, and magnetic susceptibility measurements. The thermal properties of all complexes have been investigated by TG technique. The complexes contain two monoanionic, bidentate NO ligands. It was found that all the complexes are mononuclear. Antimicrobial activities of the ligands and their complexes have been tested against five different microorganisms, and some of the complexes were found to be active against some of the microorganisms studied.     

Synthesis and structure of enaminoketones of pyrazole containing 2-thione(selenone)benzimidazolyl fragments and their zinc and cadmium complexes

New ligand systems based on 4-formyl-5-hydroxypyrazole and 1-aminobenzimidazole derivatives are synthesized. The obtained enamines and their Zn²⁺ and Cd²⁺ metal complexes of composition ML₂ were investigated using the IR, heteronuclear (¹H, ¹³C, ¹⁵N, ⁷⁷Se, ¹¹³Cd) and two-dimensional NMR spectroscopy (COSY, HSQC, HMBC). The data of physicochemical investigations and quantum-chemical calculations showed that the ligands exist in the ketoamine tautomeric form. Quantum-chemical simulation of Zn(II) and Cd(II) complexes showed that the zinc complexes adopt the pseudo-tetrahedral and the cadmium complexes pseudo-octahedral configuration.     

Synthesis and spectral studies of copper(II), nickel(II), cobalt(II) and vanadyl(II) complexes of tridentate Schiff bases of 1,2,3,5,6,7,8,8a-octahydro-3-oxo-N,1-diphenyl-5-(phenylmethylene)-2-naphthalenecarboxamide

Summary Metal(II) chelates of Schiff bases derived from the condensation of 1,2,3,5,6,7,8,8a-octahydro-3-oxo-N,1-diphenyl-5-(phenylmethylene)-2-naphthalenecarboxamide with o-aminophenol (KAAP), o-aminothiophenol (KAAT) or o-aminobenzoic acid (KAAB) have been prepared and characterized. The complexes are of the type [M(N₂X)]₂ for M = Cu^II and M(NX)₂·nH₂O for M = Ni^II, Co^II and VO^II (X = phenolic oxygen, thiophenolic sulphur or carboxylic oxygen; n = 0 or 2). Conductivity data indicate that the complexes are non-ionic. The Schiff bases behave as dibasic tridentate ligands in their copper(II) complexes and as monobasic bidentate ligands in their nickel(II), cobalt(II) and vanadyl(II) complexes. The subnormal magnetic moments of the copper(II) complexes are ascribed to an antiferromagnetic exchange interaction arising from dimerization. Nickel(II) and cobalt(II) complexes are trans octahedral whereas vanadyl(II) complexes are square pyramidal     

Preparation and properties of anionic transition metal complexes containing triheterocarbenium ions

Summary Thermally stable anionic tetracarbonylcobalt complexes containing triheterocarbenium ions, [Co(CO)₄]^–[cation]⁺, have been synthesized by the ion exchange reaction of [Co(CO)₄]^–PPN⁺ with the corresponding carbenium ions. Similar molybdenum complexes containing cyclopentadienyl and carbonyl ligands were also prepared. The complexes were characterized by elemental analyses and by i.r. and n.m.r. spectroscopies. The ionic structures of the complexes are confirmed on the basis of their large electric conductivities.     

Spin-State Variations of Iron(III) Complexes with Tetracarbene Macrocycles

Starting from their six-coordinate iron(II) precursor complexes [L^8RFe(MeCN)]²⁺, a series of iron(III) complexes of the known macrocyclic tetracarbene ligand L^8H and its new octamethylated derivative L^8Me, both providing four imidazol-2-yliden donors, were synthesized. Several five- and six-coordinate iron(III) complexes with different axial ligands (Cl⁻, OTf⁻, MeCN) were structurally characterized by X-ray diffraction and analyzed in detail with respect to their spin state variations, using a bouquet of spectroscopic methods (NMR, UV/Vis, EPR, and ⁵⁷Fe Mößbauer). Depending on the axial ligands, either low-spin (S=1/2) or intermediate-spin (S=3/2) states were observed, whereas high-spin (S=5/2) states were inaccessible because of the extremely strong in-plane σ-donor character of the macrocyclic tetracarbene ligands. These findings are reminiscent of the spin state patterns of topologically related ferric porphyrin complexes. The ring conformations and dynamics of the macrocyclic tetracarbene ligands in their iron(II), iron(III) and μ-oxo diiron(III) complexes were also studied.     

Copper(II)–nickel(II) complexes of novel 1,9-dioxa-3,6-dithiacyclotridecane-10,12-dione and 1,4-dioxa-7,10-dithiacyclododecane-2,3-dione ligands

1,9-Dioxa-3,6-dithiacyclotridecane-10,12-dione (L¹), and 1,4-dioxa-7,10-dithiacyclododecane-2,3-dione, (L²), two novel ligands, and their mono- and di-nuclear copper(II) and/or nickel(II) complexes have been prepared and characterized by elemental analyses, ¹H- and ¹³C-n.m.r., i.r., magnetic moments and mass spectral studies. Elemental analyses, stochiometric and spectroscopic data on the complexes indicate that the metal ions are coordinated to the nitrogen, oxygen and sulphur atoms and the data support the proposed structure for the diones and their mono–dinuclear copper(II) complexes. Moreover, copper(II) complexes of the dione ligands have a 1:1 metal:ligand ratio.     

Polydentate Schiff-base ligands and their Cd(II) and Cu(II) metal complexes: synthesis,characterization, biological activity and electrochemical properties

Synthesis, characterization, microbiological activity and electrochemical properties of the Schiff-base ligands A¹–A⁵ and their Cd(II) and Cu(II) metal complexes are reported. The ligands and their complexes have been characterized by elemental analysis, FT–IR, UV–Vis, ¹H- and ¹³C-NMR, mass spectra, magnetic susceptibility and conductance measurements. In the complexes, all the ligands are bidentate, the oxygen in the ortho position and azomethine nitrogen atoms of the ligands coordinate to the metal ions. The keto-enol tautomeric forms of the Schiff-base ligands A¹–A⁵ have been investigated in polar and non-polar organic solvents. Antimicrobial activity of the ligands and metal complexes were tested using the disc diffusion method and the chosen strains include Bacillus megaterium and Candida tropicalis. The electrochemical properties of the ligands A¹–A⁵ and their Cu(II) metal complexes have been investigated at different scan rates (100–500?mV?s^?1) in DMSO.     

Synthesis and Characterization of New Macrocyclic Cu（Ⅱ） Complexes from Various Diamines, Copper（Ⅱ） Nitrate and 1,4-Bis（2-formylphenoxy）butane

Six new macrocyclic complexes were synthesized by a template reaction of 1,4-bis（2-formylphenoxy）butane with diamines and Cu（NO3）2·3H2O and their structures were proposed on the basis of elemental analysis, FT-IR, UV-Vis, magnetic susceptibility measurements, molar conductivity measurements and mass spectra. The metal to ligand molar ratios of the Cu（Ⅱ） complexes were found to be 1 ： 1. The Cu（Ⅱ） complexes are 1 ： 2 electrolytes as shown by their molar conductivities （∧m） in DMF at 10^-3 mol·L^-1. Due to the existence of free ions the Cu（Ⅱ） complexes are electrically conductive. Their configurations were proposed to be probably distorted octahedral.     

Unusual deactivation in the asymmetric hydrogenation of itaconic acid

The formation of unusual Rh(III) substrate complexes from [Rh(DIPAMP)(MeOH)₂]BF₄ and itaconic acid has been detected which leads to the deactivation of the catalyst. The influence of different parameters on the formation of such complexes, namely substrate concentration, reaction time, temperature, acidic and basic additives, was investigated with different NMR methods. Two different Rh(III) substrate complexes are formed whose ratio is strongly dependent on substrate concentration and reaction time. The pH value of the solution shows a strong influence on the chemical shifts of the ³¹P NMR signals of such complexes. A catalyst-mediated esterification of itaconic acid in methanol was detected. Extended investigations provide detailed ¹H, ¹³C and ³¹P NMR data for the Rh(III) complexes and information about their stability in solution.