Structural studies on new copper(II) phenylhydrazoacetylacetone isonicotinoyl hydrazone complexes

Summary Copper(II) phenylhydrazoacetylacetone isonicotinoyl hydrazone complexes were prepared at two different pHs and characterized by elemental analysis and various physical techniques. In neutral solutions monoligand complexes (1) and (2) were obtained, but the bisligand complex (3) was obtained from solution at pH 10. The ligand H₂L behaved either as monobasic bidentate or dibasic tridentate towards cupric ions. Magnetic and spectral data suggest square planar structures for [CuL·H₂O]·H₂O but an octahedral structure for [Cu(HL)₂·2H₂O]·3H₂O.Author to whom all correspondence should be directed.     

E.s.r. and electrochemical studies of four- and five-coordinate copper(II) complexes containing mixed ligands

Heterocyclic base adducts of salicylaldehyde N(4)- cyclohexylthiosemicarbazone(H2L) copper(II) complexes have been synthesized and characterized. I.r., electronic and e.s.r. spectra of the complexes, as well as i.r., electronic and 1H- and 13C-n.m.r. spectra of the thiosemicarbazone have been obtained. Based on e.s.r. studies, all possible parameters have been calculated. The g values, calculated for all the complexes in frozen solution, indicate the presence of the unpaired electron in the dx2−y2 orbital. The metal–ligand bonding parameters evaluated showed strong in-plane σ- and in-plane π-bonding. The magnetic and spectroscopic data indicate a square-planar geometry for the four-coordinate and a distorted square-pyramidal structure for the five-coordinate complexes. From cyclic voltammetric data quasireversible copper(II)/copper(I) couples are observed for the complexes. This revised version was published online in June 2006 with corrections to the Cover Date.     

Spectral and thermal studies on copper(II) complexes of acenaphthaquinonemono(4-methylquinolinyl) hydrazone

Cu(II) complexes of acenaphthaquinonemono(4-methylquinolinyl)hydrazone (AMH) of general composition [CuLX₂] (whereL=AMH;X=Cl, Br, I, OAc or NO₃) with the exception of sulphato complex, where the composition is found to be [CuLSO₄]₂ have been synthesized and characterized by elemental analyses, magnetic moment measurements, conductivity measurements, IR, electronic and EPR spectral techniques and by thermal analysis. A planar geometry is indicated for all the complexes. TG curves show one step decomposition of complexes and formation of CU₂O at the end of the step.One of the author (P.K.S.) is thankful to UGC, New Delhi (India), for providing financial assistance and is also indebted to the Department of Chemistry, University of Delhi, Delhi (India) for providing the necessary laboratory facilities.     

E.p.r. and spectroscopic studies of configurational changes in 1,4-diazacycloheptane copper(II) complexes

Summary E.p.r. and spectroscopic studies of bis(1,4-diazacycloheptane)copper(II) perchlorate, bromobis(1,4-diazacycloheptane)copper(II) perchlorate and dibromo-bis(1,4-diazacycloheptane)copper(II), were carried out in MeNO₂, DMSO and H₂O solutions as well as in the polycrystalline state. The ligation of bromide ion to bis(1,4-diazacycloheptane)copper(II) along thez-axis was investigated. The e.p.r. spectra are explained in terms of energy changes involving the electronic ground state and the lowest excited state as a function of ligation of nucleophiles to the metal atom along thez-axis. In the polycrystalline state, the weaker the apical interaction (square-planar species) the lower theg-value and the higher the copper(II) hyperfine coupling constant. In the liquid state, theg-values observed in non-coordinating solvents such as MeNO₂ are similar to those for the polycrystalline material suggesting structural similarity in the two states. The electronic absorption maxima for the three complexes in the liquid state shift to higher energy with an increase in tetragonal distortion around copper(II). In strongly coordinating solvents the e.p.r. spectra and absorption maxima are independent of the anion present. The increasing strength of solvation results in an increase in the wavelength of the optical transition and theg-values, and a decrease in the copper(II) hyperfine coupling constant. It appears that an increase in the basicity of the solvent has the same effect on thed-orbital energy levels and on the unpaired electron density on copper(II)_as does increasing the electronegativity of the substituents on the ligand.     

An e.s.r. study of copper(II) complexes of N-hydroxyalkylsalicylideneimines

X-band e.s.r. spectra of copper(II) complexes of empirical formula Cu(Sal.NCH2CH2O)X (where X= H2O, py or Cl) and [Cu(Sal.NCH2CH2CH2O)]2 (Sal.N= OC6H4CHN) in solid and solution states at room temperature and at 77K are reported. In frozen solution at 77K the spectra show axial symmetry with a dx2−y2 ground state. The in-plane π-bonds show a moderate degree of covalence, while the out-of-plane π-bonds possess ionic character. The orbital populations of these complexes are 70.9, 81.3, 93.3 and 82.4% respectively, indicating a dx2−y2 ground state. This revised version was published online in June 2006 with corrections to the Cover Date.     

Structures of mixed ligand copper(II) complexes coordinating through S,O and N. E.p.r. studies

Summary The formation of near square planar mixed ligand Cu^II complexes with diethyldithiocarbamate (dtc) as one of the ligands and 8-hydroxyquinolinate (Hy) or salicylaldehydate (Sal) as the second ligand by exchange reactions, has been detected by e.p.r. spectroscopy. The concentrations of the mixed ligand complexes in the reaction mixtures are small compared to those of the reactants. Six different tests were used to identify the m₁=3/2,⁶³Cu hyperfine transition of the near square planar complexes, based upon the relative concentrations of the different Cu^II species in the reaction mixture, ligand hyperfine structures, the minium linewidths observed in a temperature dependent study and the isotropic g₀ estimated from the e.p.r. spectra in solution.     

Synthesis,spectroscopy and thermal analysis of copper(II) hydrazone complexes

The chelating behavior of some hydrazones towards Cu(II) has been investigated. The isolated complexes were characterized by elemental analysis, magnetic moment, spectra (electronic, IR and ms) and thermal measurements. The IR spectra showed that the ligands are deprotonated in the complexes as bidentate, tridentate and binegative tridentate. Protonation constants of the ligands and the stability constants of their Cu(II) complexes were calculated. Square-planar, square-pyramidal, tetrahedral and/or distorted octahedral structures are proposed. The TGA data help to confirm the chemical formula of the complexes and indicated the steps of their thermal degradations.     

Chemical properties,magnetic and e.p.r. studies of pyrazole copper(II) complexes

Summary Copper chloride methylpyrazole complexes have been studied and their quantitative composition and physicalchemical properties determined. On the basis of spectroscopic, electron paramagnetic resonance (c.p.r.) and magnetic studies, the structures of the complexes occurring in solids and the ethanol solutions are discussed. Four- and six-coordinate Cu-pyrazole complexes have been distinguished and the bridging properties of 3,5-demethylpyrazole ligand rationalized.     

Spectroscopic studies on three mixed-ligand copper(II) complexes

The mixed-ligand complexes [Cu(den)en](ClO₄)₂, [Cu(den)Pn](ClO₄)₂ and [Cu(den)tn](ClO₄)₂ (where den = diethylenetriamine, en = ethylenediamine, Pn = 1,2-diaminopropane, and tn = 1,3-diaminopropane) have been synthesized, and their IR, electronic and ESR spectral properties have been studied to understand the stereochemistry of these complexes both in the solid state and in DMF (dimethylformamide) or pyridine solutions. The metal appears to be five-coordinate in the solid state, formed with five nitrogens of the mixed ligand, and is found to change in solution, probably due to the attachment of a solvent molecule in the sixth coordination position. The equatorial and axial bond strengths are estimated in the solutions.     

Structural and magnetic studies on copper(II) azido complexes

The azide ligand has been receiving intense attention in the rapid growth of literature in the field of molecular magnetism. Primarily, azide ion functions as a bridging ligand and magnetic coupler of paramagnetic metal ions. This review is centered on the study of diverse structural and magnetic properties of copper(II) azido complexes. Some of the trends identified could serve as a privileged starting point for the further development of this promising area.     

Manganese(II) complexes of substituted thio-and selenosemicarbazones of 2-acetylpyridine: E.s.r., magnetic and electronic spectral studies

Summary Manganese(II) bis(ligand) complexes of substituted thiosemicarbazones and selenosemicarbazones derived from 2-acetylpyridine of general formula [MnL₂] (where L=deprotonated ligand) have been synthesized and characterised by elemental analyses, electronic spectra in solution, i.r. spectra, magnetic measurements and e.s.r. spectra recorded in polycrystalline state and in solution at room temperature and 77K. The terdentate character of the ligands in all the complexes is inferred from i.r. spectra. The electronic spectra along with e.s.r. spectra suggest an octahedral environment around the manganese(II). The metal-ligand bonds are moderately covalent. Thus all the complexes reported here are six-coordinated and high-spin octahedral.     

Synthesis and electronic,magnetic and E.s.r. studies of some bimetallic alkoxides of copper(II) with niobium(V) and Tantalum(V)

Summary Novel bimetallic alkoxides of copper(II) of the type Cu[M(OPr-i)₆]₂ (M = Nb or Ta) have been synthesised by the interaction of CuCl₂ (1 mol) with K[M(OPr-i)₆] (2 mol). These bimetallic isopropoxides undergo facile alcohol interchange with primary alcohols such as MeOH, EtOH,n-PrOH andn-BuOH. However, witht-BuOH, the reaction cannot be driven to completion even under prolonged continuous azeotropic fractionation of the liberatedi-PrOH and the final product corresponded in analysis to Cu[Ta(OPr-i)₂(OBu-t)₄]₂.I.r., electronic and electron spin resonance spectral and magnetic susceptibility measurements indicate a distorted octahedralD _4h geometry for copper(II) in these bimetallic alkoxides.     

Synthetic, spectral and solution studies on imidazolate-bridged copper(II)-copper(II) and copper(II)-zinc(II) complexes

Synthesis, spectral and solution studies on 2-ethyl imidazolate-bridged (2-EtIm) homo-binuclear copper(II)-copper(II) and hetero-binuclear copper(II)-zinc(II) homologue are described. Magnetic moment values of homo-binuclear complexes indicate that the imidazolate group can mediate antiferromagnetic interactions. Optical spectra of hetero-binuclear complex at varying pH values suggest that the imidazolate-bridged complex is stable over the pH-range 7.15–10.0.     

X-band e.p.r. spectra of mixed-ligand copper(II) complexes

E.p.r. spectra of [Cu(et2dtc)2], Na[Cu(asp/glut)(et2dtc)] and Na2[Cu(asp/glut)(et2dtc)2] in the polycrystalline state have been recorded and discussed. The complexes display an antiferromagnetic exchange interaction, increasing in the order: Na2[Cu(asp/glut)(et2dtc)2] < Na[Cu(asp/glut)(et2dtc)] < [Cu(et2dtc)2] This revised version was published online in June 2006 with corrections to the Cover Date.     

Spectroscopic studies of copper(II) and iron(II) complexes of adriamycin

The complexes of adriamycin (ADM) with Cu(II) and Fe(II) have been studied by visible absorption, circular dichroism (CD) and fluorescence spectra, respectively. In Tris buffer at pH 7.0, either metal ions forms a single species with adriamycin: Cu(ADM)2 or Fe(ADM)3. Interaction of these two complexes with various biological molecules has been examined. It is shown that some amino acids, glutathione and albumin are able to remove the Cu(II) ion from Cu(II)-ADM complex, releasing the free drug. However, Fe(II)-ADM keeps in an undissociated form under the same conditions. The possibility of Fe(II) ADM as a new alternative drug has been discussed.     

Chromotropism studies on copper(II) compounds. Part II. Dinuclear copper(II) complexes with triply-bridged hydroxo,acetate, and halo ligands

Abstract

Two triply-bridged dinuclear copper(II) complexes of formula [LCu(μ-OH)(μ-OAc)(μ-X)CuL]X?0.5H₂O where L is a bidentate ligand of N-(pyridine-2-ylmethyl)propane-2-amine and X=Cl, 1 and Br, 2 were synthesized and characterized by elemental analyses, spectroscopic techniques (IR, UV–Vis, EPR), thermal analysis, conductance measurements, and single-crystal X-ray structure determination. The structures of both complexes are similar. The complexes show a distorted square-pyramidal arrangement around each copper(II) ion with a CuN₂O₂X chromophore in which both copper(II) ions are connected by a hydroxo bridge and a triatomic syn-syn carboxylato bridge in equatorial positions and a halide ion bridge at the axial site. The chromotropism behavior of the complexes, including solvato-, thermo-, and halochromism, were investigated in detail. Their halochromism was investigated in the pH range of 2.0–11.0 by visible absorption spectroscopy. The reversible color variations from blue to colorless are attributable to deprotonation and protonation of the ligands. The complexes show reversible thermochromism in solution due to dissociation and recombination of ligands to copper ions.     

Thermal studies on purine complexes. I. Thermal behaviour of some xanthine complexes of cobalt(II), copper(II) and cadmium(II)

Cobalt, copper and cadmium xanthinate tetrahydrates have been prepared in aqueous medium, and characterized on the basis of elemental analysis, IR and ¹HNMR studies. The thermal behaviour of these compounds has been studied using TG, DTG and DSC techniques. Heats of dehydration have been calculated from DSC curves.     

Synthesis,characterization and biomimetic oxygenations of manganese(II), iron(III) and copper(II) pyridyl hydrazone complexes

The preparation and characterization of MnII, FeIII and CuII complexes of three tridentate pyridyl hydrazones are reported. The ligands were prepared via Schiff base condensation of 6-chloro-2-hydrazopyridine with alpha-formyl-(L1), alpha-acetyl-(L2), or alpha-benzoyl-(L3) pyridine. The structural characterization of the compounds prepared was based on elemental analyses, electrical conductance and magnetic moment measurements, 1H-n.m.r., i.r., u.v.-vis. and e.s.r spectroscopic methods. The overall structure and reactivity of the metal chelates critically depend on the ligand substituents within the carbonyl moiety. Octahedral and tetrahedral monomeric species were proposed for MnII complexes, and an octahedral environment for the FeIII complexes. Regarding the copper(II) complexes, a monomeric square-planar and a dimeric structure with a chloride bridge in square-pyramidal geometry were suggested. In the presence of molecular oxygen, MnII and CuII complexes catalyse the oxidative transformation of catechol (benzene-1,2-diol) to the corresponding o-benzoquinone. Iron(III) complexes catalyse the aerobic oxidation of catechol to the intradiol cleavage product. The catalytic activity has been correlated with the Lewis acidity of the metal centres created according to the nature of the ligand substituents. The probable mechanistic implications of the catalysed oxidation reactions are discussed. This revised version was published online in June 2006 with corrections to the Cover Date.