Spectroscopic approach in characterization of chromium(III), manganese(II), iron(III) and copper(II) complexes with a nitrogen donor tetradentate, 14-membered azamacrocyclic ligand

The complexes of Cr(III), Mn(II), Fe(III) and Cu(II) were synthesized with the macrocyclic ligand i.e. 2,3,9,10-tetraketo-1,4,8,11-tetraazacyclotetradecane. The ligand was prepared by the [2 + 2] condensation reaction of diethyloxalate and 1,3-diamino propane. These complexes were found to have the general composition M(L)X3 and M'(L)X2 [where M = Mn(II) and Cu(II), M' = Cr(III) and Fe(III), L = ligand (N4) and X = Cl-, NO3-, 1/2SO4(2-) and [CH3COO-]. The ligand and its transition metal complexes were characterized by the elemental analyses, molar conductance, magnetic susceptibility, mass, IR, electronic, and EPR spectral studies. On the basis of IR, electronic and EPR spectral studies an octahedral geometry has been assigned for Cr(III), Mn(II) and Fe(III) and a tetragonal geometry for Cu(II) complexes.     

Chromium(III), manganese(II), iron(III), cobalt(II), nickel(II) and copper(II) complexes with a pentadentate, 15-membered new macrocyclic ligand

Complexes of Cr^III, Mn^II, Fe^III, Co^II, Ni^II and Cu^II containing a macrocyclic pentadentate nitrogen–sulphur donor ligand have been prepared via reaction of a pentadentate ligand (N₃S₂) with transition metal ions. The N₃S₂ ligand was prepared by [1 + 1] condensation of 2,6-diacetylpyridine with 1,2-di(o-aminophenylthio(ethane. The structures of the complexes have been elucidated by elemental analyses, molar conductance, magnetic susceptibility measurements, i.r., electronic and e.p.r. spectral studies. The complexes are of the high spin type and are six-coordinate.     

Spectroscopic studies on chromium(III), manganese(II), cobalt(II), nickel(II) and copper(II) complexes with hexadentate nitrogen-sulfur donor [N(2)S(4)] macrocyclic ligand

Complexes of transition metals have been synthesized with hexadentate ligand (2,6-bis(((2-mercaptophenyl)thio)methyl)pyridinato)metal(II). These complexes have been synthesized via the two step template reaction by using the benzene dithiol, 2,6-bis(chloro)methyl pyridine and corresponding metal salt as key raw materials. The structures of the complexes have been elucidated on the basis of elemental analysis, molar conductance measurements, magnetic susceptibility measurements, IR, electronic and EPR spectral studies. All of the complexes were found to possess six-coordinated geometry and are of high spin type.     

Chromium(III), manganese(II), cobalt(II), nickel(II), copper(II) and palladium(II) complexes of a 12-membered tetraaza [N4] macrocyclic ligand

Cr^III, Mn^II, Co^II, Ni^II, Cu^II and Pd^II complexes of the macrocyclic ligand, 2,3,5,8,9,11 hexamethyl-1,4,7,10 tetraaza- cyclododeca-1,3,7,9 tetraene (DADAP), have been synthesized and characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, i.r., electronic and e.p.r. spectral studies. These spectral studies suggest an octahedral geometry for the Cr^III, Mn^II and Co^II, square planar geometry for Ni^II and Pd^II and tetragonal geometry for Cu^II complexes.     

Spectroscopic characterization and EPR spectral studies on transition metal complexes with a novel tetradentate, 12-membered macrocyclic ligand

Complexes of Cr(III), Mn(II), Co(II), Ni(II) and Cu(II) containing a tetradentate macrocyclic N-donor ligand have been prepared via template reaction of 2,3-pentanedione, ethylene-di-ammine and transition metal ions. The complexes have been characterized on the basis of the elemental analysis, molar conductance, magnetic moment susceptibility, IR, electronic and EPR spectral studies. The complexes are of high spin type and possess four coordinate tetrahedral five coordinate square pyramidal and six coordinated octahedral/tetragonal geometry.     

Spectroscopic studies of transition metal complexes with a N-donor tetradentate(N4) 12-membered macrocylic ligand

Chromium(III), manganese(II), iron(III), cobalt(II), nickel(II), copper(II), ruthenium(III), iridium(III), palladium(II) and platinum(II) complexes were synthesized with a 12-membered 1,4,7,10-tetraazadodeca-5,6,11,12-tetraene macrocylic ligand (L) and characterized by elemental analysis, molar conductance, magnetic susceptibility, IR, electronic, EPR and M?ssbauer [Fe(III)] spectral studies. The molar conductance measurements of all the complexes in DMF solution correspond to non-electrolytic nature for M(L)Cl2 complexes [where M=Mn(II), Co(II), Ni(II), Cu(II)], 1:1 electrolytes for M'(L)Cl3 complexes [where M'=Cr(III), Fe(III), Ru(III) and Ir(III)] and 1:2 electrolytes for M'(L)Cl2 complexes [where M'=Pd(II) and Pt(II)]. Thus, the complexes may be formulated as [M(L)C1(2)], [M'(L)C1(2)]C1 and [M'(L)]C1(2), respectively [where L=ligand]. All complexes were of the high-spin type and found to have six-coordinate octahedral geometry except the Pd(II) and Pt(II) complexes which were four coordinate, square planar and diamagnetic.     

Polynuclear complexes of chromium(III), copper(II) or nickel(II) with thiocyanate as a bridging ligand

Novel complexes of the type [CuL2]3[Cr(NCS)6]2·xH2O (L = 2,2-bipyridine (bpy), x = 0; L = o-phenanthroline (phen), x = 1), [Cu(dien)]3[Cr(NCS)6]2·3H2O (dien=diethylenetriamine) or [Ni(phen)2]3[Cr(NCS)6]2· 2H2O have been prepared and studied by elemental analyses, i.r. spectra and magnetic measurements. Some of the complexes have been characterized by temperature-dependent magnetic susceptibilities, and weak antiferromagnetic exchange interaction was found for [Cu-(phen)2]3[Cr(NCS)6]2·H2O and [Ni(phen)2]3[Cr(NCS)6]2· 2H2O. Physico-chemical studies account for the polymeric structure, with thiocyanate bridges between Cu or octahedral Ni and octahedral Cr (chromophore CrN6).     

Syntheses,crystal structures,and antibacterial activities of manganese(III), nickel(II), and copper(II) complexes containing a tetradentate Schiff base

Three new mononuclear Schiff-base complexes, namely [Mn(L)Cl] (1), [Ni(L)] (2), and [Cu(L)] (3), where L?=?anion of [N,N′-bis(2-hydroxybenzophenylidene)]propane-1,2-diamine, have been synthesized by reacting equimolar amounts of the respective metal chloride and the tetradentate Schiff base, H₂L, in methanol. The complexes have been characterized by microanalytical, spectroscopic, single-crystal X-ray diffraction, and other physicochemical studies. Structural studies reveal that 1 adopts a distorted square-pyramidal geometry whereas 2 and 3 are isotypic with distorted square-planar geometries. The antibacterial activities of 1–3 along with their Schiff base have been tested against some Gram(+) and Gram(?) bacteria.     

Synthesis and spectral studies on mononuclear complexes of chromium(III) and manganese(II) with 12-membered tetradentate N2O2, N2S2 and N4 donor macrocyclic ligands

Complexes of Cr^III and Mn^II of general formula [Cr(L)X₂] X and [Mn(L)X₂] respectively were prepared from N₂O₂, N₂S₂ and N₄ donor macrocyclic ligands. The complexes have been characterized by elemental analysis, molar conductance measurements, spectral methods (i.r, mass, ¹H-n.m.r, electronic spectra and e.p.r.) and magnetic measurements. The macrocyclic ligands have three different donating atom cavities, one with two unsaturated nitrogens and the other two have saturated nitrogen, oxygen and sulphur atoms. The effect of different donor atoms on the spectra and ligand field parameters is discussed. All the complexes show magnetic moments corresponding to a high-spin configuration. On the basis of spectral studies a six coordinated octahedral geometry may be assigned to these complexes.     

Spectro-thermal characterization of chromium(III) and manganese(II) complexes with carboxyamide

Complexes of Cr(III) and Mn(II) with N′,N″-bis(3-carboxy-1-oxopropanyl) 2-amino-N-arylbenzamidine (H₂L¹) and N′,N″-bis(3-carboxy-1-oxophenelenyl) 2-amino-N-arylbenzamidine (H₂L²) have been synthesized and characterized by various physico-chemical techniques. The vibrational spectral data are in agreement with coordination of amide and carboxylate oxygen of the ligands with the metal ions. The electronic spectra indicate octahedral geometry around the metal ions, supported by magnetic susceptibility measurements. The thermal behavior of chromium(III) complexes shows that uncoordinated nitrate is removed in the first step, followed by two water molecules and then decomposition of the ligand; manganese(II) complexes show two waters removed in the first step, followed by removal of the ligand in subsequent steps. Kinetic and thermodynamic parameters were computed from the thermal data using Coats and Redfern method, which confirm first order kinetics. The thermal stability of metal complexes has been compared. X-ray powder diffraction determines the cell parameters of the complexes.     

Investigations of chromium(III), manganese(III), tin(II) and lead(II) dithiocarbamate complexes

Piperidine-, morpholine-4-, N-methylpiperazine-4- and thiornorpholine-4-carbodithioate complexes of chromium(III), manganese(III), tin(II) and lead(II) are prepared and characterized by chemical analyses, spectroscopic methods (I.R. and electronic spectra), magnetic susceptibilities, conductivity measurements and mass spectra. The complexes are of the type M(R₂dtc)n, where n is the oxidation number of the metal ion. Where possible a tentative stereochemistry of the complexes is discussed on the basis of the results obtained. In all the complexes the dithiocarbamate ligands show bidentate behaviour.     

Molecular and electronic structure of square-planar nickel II, nickel III and nickel III pi-cation radical complexes with a tetradentate o-phenylenedioxamidate redox-active ligand

The molecular and electronic structures of the electron transfer series of four-coordinate square-planar nickel complexes with the ligand o-phenylenebis(N'-methyloxamidate), [NiL]z (z = 2-, 1-, 0), have been evaluated by DFT and TDDFT calculations, and most of their experimentally available structural and spectroscopic properties (X. Ottenwaelder et al., Dalton Trans., 2005, DOI: 10.1039/b502478a) have been reasonably reproduced at the B3LYP level of theory. The anionic species [NiL]2- and [NiL]- are genuine low-spin nickel II and nickel III complexes with diamagnetic singlet (S = 0) and paramagnetic doublet (S = 1/2) states, respectively. The nickel III complex presents shorter Ni-N(amidate) bond distances (1.85-1.90 A) than the parent nickel II complex (1.88-1.93 A) and characteristic LMCT bands in the NIR region (lambda max = 794 and 829 nm) while the analogous MLCT bands for the nickel(II) complex are in the UV region (lambda max = 346 and 349 nm). The neutral species [NiL] is a nickel III o-benzosemiquinonediimine pi-cation radical complex with a diamagnetic singlet (S = 0) and a paramagnetic triplet (S = 1) states fairly close in energy but fundamentally different in orbital configuration. The singlet metal-radical ground state results from the antiferromagnetic coupling between the 3d(yz) orbital of the Ni III ion (S(M) = 1/2) and the pi(b) orbital of the benzosemiquinone-type radical ligand (S(L) = 1/2), which have a large overlap and thus strong covalent bonding. The triplet metal-radical excited state involves the ferromagnetic coupling between the Ni III 3d(zx) orbital and the benzosemiquinone-type pi(b) orbital, which are orthogonal to each other. The singlet and triplet states of the nickel III pi-cation radical complex possess characteristic quinoid-type short-long-short alternating sequence of C-C bonds in the benzene ring, as well as intense MLCT transitions in the VIS (lambda max = 664 nm) and NIR (lambda max = 884 nm) regions, respectively.     

Novel repaglinide complexes with manganese(II), iron(III), copper(II) and zinc(II): Spectroscopic,DFT characterization and electrochemical behaviour

Novel transition metal complexes with the repaglinide ligand [2-ethoxy-4-[N-[1-(2piperidinophenyl)-3-methyl-1-1butyl] aminocarbonylmethyl]benzoic acid] (HL) are prepared from chloride salts of manganese(II), iron(III), copper(II), and zinc(II) ions in water-alcoholic media. The mononuclear and non-electrolyte [M(L)₂(H₂O)₂]?nH₂O (M = Mn²⁺, n = 2, M = Cu²⁺, n = 5 and M = Zn²⁺, n = 1) and [M(L)₂(H₂O)(OH)]?H₂O (M = Fe³⁺) complexes are obtained with the metal:ligand ratio of 1:2 and the L-deprotonated form of repaglinide. They are characterized using the elemental and molar conductance. The infrared, ¹H and ¹³C NMR spectra show the coordination mode of the metal ions to the repaglinide ligand. Magnetic susceptibility measurements and electronic spectra confirm the octahedral geometry around the metal center. The experimental values of FT-IR, ¹H, NMR, and electronic spectra are compared with theoretical data obtained by the density functional theory (DFT) using the B3LYP method with the LANL2DZ basis set. Analytical and spectral results suggest that the HL ligand is coordinated to the metal ions via two oxygen atoms of the ethoxy and carboxyl groups. The structural parameters of the optimized geometries of the ligand and the studied complexes are evaluated by theoretical calculations. The order of complexation energies for the obtained structures is as follows:

$$Fe(III) complex < Cu(II) complex < Zn(II) complex < Mn(II) complex.$$

The redox behavior of repaglinide and metal complexes are studied by cyclic voltammetry revealing irreversible redox processes. The presence of repaglinide in the complexes shifts the reduction potentials of the metal ions towards more negative values.

     

Synthesis,characterization and susceptibility of bacteria against Sulfamethoxydiazine complexes of copper(II), zinc(II), nickel(II), cadmium(II), chromium(III) and iron(III)

Complexes of sulfamethoxydiazine with Cu(II), Zn(II), Ni(II), Cd(II), Cr(III) and Fe(III) have been synthesized and characterized on the basis of conductivity measurements, elemental analyses, UV, IR, ¹H?NMR and thermal studies. It is shown that sulfamethoxydiazine behaves as a bidentate ligand, binding the metal ion through the sulfonyl oxygen and sulfonamide nitrogen. In vitro susceptibility tests of these complexes against Escherichia coli, Bacillus subtilis, Proteus vulgaris and Staphylococcus aureus were carried out. The results show that the antibacterial activities of the complexes of Zn(II), Cu(II), Cr(III) and Fe(III) are, in general, stronger than that of sulfamethoxydiazine, while the complexes of Cd(II) and Ni(II) are less active.     

EPR, IR and electronic spectral studies on Mn(II), Co(II), Ni(II) and Cu(II) complexes with a new 22-membered azamacrocyclic [N4] ligand

The complexes of transition metal ions with an azamacrocyclic tetradentate nitrogen donor [N4] ligand viz. 2,6,12,16,21,22-hexaaza;3,5,13,15-tetramethyltricyclo[15.3.1.1(7-11)] docosa;1(21),2,5,7,9,11(22),12,15,17,19-decaene (L) have been synthesized. All the complexes were found to have general composition M(L)X2 [where M = manganese(II), cobalt(II), nickel(II) and copper(II) and X = Cl- & NO3-]. All the complexes are characterized by the elemental analysis, molar conductance measurements, magnetic susceptibility measurements, mass, 1H NMR, IR, electronic, EPR spectral and cyclic voltammetric studies. An octahedral geometry was assigned for Mn(II), Co(II) and Ni(II) complexes and tetragonal for Cu(II) complexes. The biological actions of the ligand and complexes have been screened in vitro against many bacteria and pathogenic fungi to study their comparative capacity to inhibit the growth.     

Complexes of chromium(III), manganese(II) and nickel(II) with methylhydrazinecarboxylate and 1,1-dimethylhydrazinecarboxylate ligands

Summary New complexes of chromium(III), manganese(II) and nickel(II) with methylhydrazinecarboxylate (MeCz) and of manganese(II) and nickel(II) with 1,1-dimethylhydra-zinecarboxylate (Me₂Cz) were prepared by reacting salts of the metals with CO₂-saturated solutions of the hydrazines in EtOH. The compounds [Cr(MeCz)₃]·2H₂O, Ni(MeCz)₂(H₂O)₃·MMH, Mn(MeCz)₂(H₂O)₂(MMH = monomethylhydrazine) and M(Me₂Cz)₂(H₂O)₂ (M = Mn or Ni) were investigated using d.t.a., t.g.a., electronic and i.r. spectroscopy and by magnetic susceptibility measurements.     

New copper(II), manganese(III), nickel(II) and zinc(II) complexes with a chiral quadridentate Schiff base

A chiral Schiff base ligand (H₂L) was obtained by condensing 2-hydroxynaphthalene-1-carbaldehyde with substituted (1R,2R)-(–)-diaminocyclohexane. Chiral Schiff base complexes [CuL], [NiL], [ZnL] and [MnLOH] have been synthesized and characterized by elemental analyses, _M, i.r., u.v.–vis. and ¹H-n.m.r. and magnetic measurements.     

Cobalt(II), nickel(II), and copper(II) complexes of 14-membered hexaazamacrocycles: synthesis and characterization

Cobalt(II), nickel(II), and copper(II) complexes containing 5,12-di(4-bromophenyl)-7,14-dimethyl-1,2,4,8,9,11-hexaazacyclotetradeca-7,14-diene-3,10-dione (H₂L¹) and 5,12-diphenyl-7,14-dimethyl-1,2,4,8,9,11-hexaazacyclotetradeca-7,14-diene-3,10-dione (H₂L²) have been synthesized. All complexes were characterized by elemental analysis, MALDI TOF-MS spectrometry, and electronic absorption spectroscopy. The crystal structures of two compounds, [Cu₂(H₂L¹)Cl₄]_n and [NiL²], were determined by X-ray powder diffraction. In the polymeric [Cu₂(H₂L¹)Cl₄]_n, the Cu₂Cl₄ units and H₂L¹ molecules are situated on inversion centers. Each Cu(II) has a distorted trigonal-bipyramidal coordination environment formed by N and O from H₂L¹ [Cu–N 2.340(14)?Å, Cu–O 1.952(11)?Å], two bridging chlorides [Cu–Cl 2.332(5), 2.279(5)?Å] and one terminal chloride [Cu–Cl 2.320(6)?Å]. In the [NiL²] complex, the Ni(II) situated on inversion center has a distorted square-planar coordination environment formed by four nitrogens from L² [Ni–N 1.860(11), 1.900(11)?Å].     

Investigation of the oxygen affinity of manganese(II), cobalt(II) and nickel(II) complexes with some tetradentate Schiff bases

Oxygen absorption–desorption processes for square planar Mn(II), Co(II) and Mn(II) complexes of tetradentate Schiff base ligands in DMF and chloroform solvents were investigated. The tetradentate Schiff base ligands were obtained by condensation reaction of ethylenediamine with salcyldehyde, o-hydroxyacetophenone or acetylacetone in the molar ratio 1:2. The square planar complexes were prepared by the reaction of the Schiff base ligands with Mn(II) acetate, Co(II) nitrate and Ni(II) nitrate in dry ethanol under nitrogen atmosphere. The sorption processes were undertaken in the presence and absence of (pyridine) axial-base in 1:1 M ratio of (pyridine:metal(II) complexes). Complexes in DMF indicate significant oxygen affinity than in chloroform solvent. Cobalt(II) complexes showed significant sorption processes compared to Mn(II) and Ni(II) complexes. The presence of pyridine axial base clearly increases oxygen affinity.     

Syntheses, electronic structures, and EPR/UV-vis-NIR spectroelectrochemistry of nickel(II), copper(II), and zinc(II) complexes with a tetradentate ligand based on S-methylisothiosemicarbazide

Template condensation of 3,5-di-tert-butyl-2-hydroxybenzaldehyde S-methylisothiosemicarbazone with pentane-2,4-dione and triethyl orthoformate at elevated temperatures resulted in metal complexes of the type M(II)L, where M = Ni and Cu and H(2)L = a novel tetradentate ligand. These complexes are relevant to the active site of the copper enzymes galactose oxidase and glyoxal oxidase. Demetalation of Ni(II)L with gaseous hydrogen chloride in chloroform afforded the metal-free ligand H(2)L. Then by the reaction of H(2)L with Zn(CH(3)COO)(2)·2H(2)O in a 1:1 molar ratio in 1:2 chloroform/methanol, the complex Zn(II)L(CH(3)OH) was prepared. The three metal complexes and the prepared ligand were characterized by spectroscopic methods (IR, UV-vis, and NMR spectroscopy), X-ray crystallography, and DFT calculations. Electrochemically generated one-electron oxidized metal complexes [NiL](+), [CuL](+), and [ZnL(CH(3)OH)](+) and the metal-free ligand cation radical [H(2)L](+?) were studied by EPR/UV-vis-NIR and DFT calculations. These studies demonstrated the interaction between the metal ion and the phenoxyl radical.