X-band e.p.r. spectra of imidazole/imidazolate bridged polynuclear copper(II) complexes

X-band e.p.r. spectra of polycrystalline, polynuclear complexes of the type [(dien)Cu-im- Cu(dien)]n(ClO4)n and [(dien)Cu-imH- Cu(dien)]n(ClO4)2n are described, where dien = diethylenetriamine, imH and im are imidazole (and 2-methyl- and 2-ethylimidazole) respectively. All the complexes show e.p.r. spectra characteristic of S=1, which yield the value of the zero field splitting parameter, D, in the 0.030±0.001cm–1 range.     

Synthesis,magnetic moments and X-band e.p.r. spectra of binuclear and trinuclear copper(II) complexes

The imidazole-bridged binuclear copper(II) complex, [(Cl)2(imH)2Cu(imH)2Cu(bipy)(Cl)2] and the trinuclear copper (II) complex [(Cl)2(bipy)Cu(imH)2Cu(imH)2Cu(bipy)(Cl)2] have been synthesized by direct coupling between [Cu(imH)4(Cl)2] and [Cu(bipy)Cl2] in the appropriate stoichiometric ratios. The complexes show subnormal magnetic moments and e.p.r. spectra, characteristic of the triplet state. The antiferromagnetic coupling constant, J, has been obtained for both the complexes.     

Near neighbour ligand hyperfine splittings in the e.p.r. spectra of copper(II) complexes

X-band e.p.r. spectra from mixed ligand complexes Cu(btc)-(Hy), Cu(TPA)(Hy) and Cu(Sal)(TPA), have been derived from the spectra of suitable reaction mixtures in CHCl₃ at 25° C (Sal⁻ = salicyladehydate, TPA⁻ = thiopicolineanilide, Hy⁻ = 8-hydroxyquinolinate and btc⁻ =N-benzoyl-N′N′-diethylcarbamide). A digital data acquisition instrument and a personal computer were used for this purpose. The¹⁴N hyperfine splittings observed in these complexes have shown that the observed increase in spin density on the coordinating atoms of one ligand, at the expense of that on the other, is unlikely to be associated with the covalent bonding involving metal d _x ²− _y ²-orbital. Covalent bonding involving metal 4s-orbital component of the unpaired electron orbital has been suggested to be responsible for the observed changes in electron delocalization. This work was carried out during the visit of Drs Z. R. Baratova and P. M. Solozhenkin to India in 1991.     

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.     

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.     

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.     

E.p.r. spectra of mixed valence copper(II)-copper(I) systems

Summary Mixed valence (thiosemicarbazone)₂Cu^II-Cu^I complexes were prepared and their e.p.r. spectra in the polycrystalline state studied. Complexes derived from acetophenone- and propiophenonethiosemicarbazones exhibit strong copper(II)-copper(II) and copper(II)-copper(I) interactions, whereas those derived from benzyl methyl ketone and cyclohexanone show strong copper(II)-copper(I) interaction but almost no copper(II)-copper(II) interaction.     

Electronic, e.p.r., cyclic voltammetric and biological activities of copper(II) complexes with macrocyclic ligands

Eight new macrocyclic ligands have been prepared by the reaction of the precursor diketone (benzil, glyoxal, diacetyl or 2,3-pentanedione) with a diamine (thiosemicarbazide or semicarbazide). Copper(II) complexes of these ligands have been synthesized and characterized by elemental analysis, molar conductance, magnetic susceptibility, i.r., u.v.–vis, ¹H-n.m.r., mass and e.p.r. spectral studies. Mass, n.m.r. and i.r. data indicate the condensation of the diamine and diketone and the whole molecular ion structure. g-Values are calculated for all of the complexes in polycrystalline form as well as in DMSO solution. Spin Hamiltonian values and bonding parameters have also been calculated which indicates that an unpaired electron is present in the orbital. The metal-ligand bonding parameters shows strong in-plane σ sigma and in-plane π bonding. The magnetic and spectral data indicate tetragonal geometry for all of the complexes except [CuH₂L⁴]Cl₂ and [CuH₂L⁴]Cl₂ which are square planar. From c.v. data reversible Cu^II/Cu^I couples are observed for these complexes. The macrocyclic complexes show more antibacterial and antiviral activity as compared to the ligands. The antibacterial activities of the compounds were tested against S. aureus, S. subtillis and E. coli.     

Synthesis,electrochemical and e.p.r. spectral studies of binuclear copper(II) complexes with new pentadentate L-proline-based binucleating ligands

The synthesis, reduction, optical and e.p.r. spectral properties of a series of new binuclear copper(II) complexes, containing bridging moieties (OH^–, MeCO₂ ^–, NO₂ ^–, and N₃ ^–), with new proline-based binuclear pentadentate Mannich base ligands is described. The ligands are: 2,6-bis[(prolin-1-yl)methyl]4-bromophenol [H₃L¹], 2,6-bis[(prolin-1-yl)methyl]4-t-butylphenol [H₃L²] and 2,6-bis[(prolin-1-yl)methyl]4-methoxyphenol [H₃L³]. The exogenous bridging complexes thus prepared were hydroxo: [Cu₂L¹(OH)(H₂O)₂] · H₂O (1a), [Cu₂L²(OH)(H₂O)₂] · H₂O (1b), [Cu₂L³(OH)(H₂O)₂] · H₂O (1c), acetato [Cu₂L¹(OAc)] · H₂O (2a), [Cu₂L²(OAc)] · H₂O (2b), [Cu₂L³(OAc)] · H₂O (2c), nitrito [Cu₂L¹(NO₂)(H₂O)₂] · H₂O (3a), [Cu₂L²(NO₂)(H₂O)₂] · H₂O (3b), [Cu₂L³(NO₂)(H₂O)₂] · H₂O (3c) and azido [Cu₂L¹(N₃)(H₂O)₂] · H₂O (4a), [Cu₂L²(N₃)(H₂O)₂] · H₂O (4b) and [Cu₂L³(N₃)(H₂O)₂] · H₂O (4c). The complexes were characterized by elemental analysis and by spectroscopy. They exhibit resolved copper hyperfine e.p.r. spectra at room temperature, indicating the presence of weak antiferromagnetic coupling between the copper atoms. The strength of the antiferromagnetic coupling lies in the order: NO₂ N₃ OH OAc. Cyclic voltammetry revealed the presence of two redox couples Cu^IICu^II Cu^IICu^I Cu^ICu^I. The conproportionality constant K _con for the mixed valent Cu^IICu^I species for all the complexes have been determined electrochemically.     

Thermal and photochemical reactions of copper(II) dithiocarbamate mixed-ligand complexes with chloroalkanes

Thermal and/or photochemical conversion of a series of copper(II) complexes containing mixed dithiocarbamato–alcohol ligands, Cu^II(Et₂dtc)⁺ . . . Y⁻ (Y=ClO₄⁻, NO₃⁻), into Cu^II(Et₂dtc)Cl in chloroalkane/alcohol solutions, where chloroalkane=CCl₄, CHCl₃ or CH₂Cl₂ and alcohol=MeOH, EtOH or i-BuOH, proceeds in chloroalkanes. Both reactions follow a similar pathway which is more effective the stronger the acceptor properties of chloroalkanes and the weaker the coordinating abilities of alcohols are. A detailed reaction mechanism is proposed which well fits the experimental results obtained by EPR and UV–VIS spectra and quantum yields.     

Structure of copper(II) dithiocarbamate mixed-ligand complexes and their photoreactivities in alcohols

The composition of the co-ordination sphere of Cu(II) dithiocarbamate mixed-ligand complexes Cu(Et2)dtc)X (X = Cl-, Br-) and Cu(Et2)dtc)(+)...Y- (Y- = ClO4-, NO3-) is studied from the combined analysis of spectrophotometric and EPR data. The results obtained about CT-photolysis of the complexes in EtOH and i-PrOH are compared with our previous data of photolysis in chloromethane/ROH solutions. Reaction mechanism and the role of alcohol are discussed on the ground of electronic and EPR spectra and quantum yield results.     

Synthesis,crystal structure and e.p.r. spectra of one-dimensional manganese(II) 3,5-dinitrobenzoate dihydrate

The crystal structure of catena-diaquatetrakis(₂-3,5-dinitrobenzoato-O,O)manganese(II) has been determined by X-ray diffraction. It consists of a chain with the 3,5-dinitrobenzoate group acting in the syn-anti ₂-O,O-bridging fashion, in which the Mn^II atom is octahedrally coordinated by two aqua ligands [2.162(3) Å] and four carboxy oxygen atoms [Mn—O = 2.114(3) and 2.221(3) Å]. The X-band e.p.r. spectra of this complex show a hyperfine structure due to Mn^II (I = 5/2) with a splitting factor (A) of 97 G at 5 K and 93 G at 19 K, respectively.     

Ternary mixed-ligand copper(II) complexes with chiral aminophosphonic acids and amino acids

Ternary mixed-ligand complexes of divalent copper, where one ligand is an -aminoalkylphosphonic acid (APA) and the second ligand is L-phenylalanine, L-tyrosine, or L-dihydroxyphenylalanine, are studied by potentiometric titration in aqueous medium at 25°C and =0.1. A maximum in the formation of the ternary complexes is exhibited at pH 7–8. The log K_st for the complexes formed and the statistical parameters characterizing the ternary complexes logK and logX are determined. The effect of substituents on the -carbon atom of the -APA and of hydroxy groups on the phenyl substituent of the -amino acids on the nature of the distribution of the complexes formed is studied.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2482–2486, November 1989.The authors thank V. P. Solov'ev for helpful discussions.     

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.     

Charge-transfer photolysis of copper(II) dithiocarbamate mixed-ligand complexes in toluene/alcohol solutions

Charge-transfer (CT)-photolysis of Cu(II) dithiocarbamate mixed-ligand complexes Cu(II)(Et2dtc)X (X = Cl-, Br-) and Cu(II)(Et2dtc)(+)...Y- (Y = ClO4-, NO3-) has been studied in toluene/ROH and compared with our previous data obtained in chloromethane/ROH solutions, where chloromethane = CCl4, CHCl3 or CH2Cl2 and ROH = MeOH, EtOH, i-PrOH or i-BuOH. An EPR evidence is obtained about the formation of a new copper(II) dithiocarbamate mixed-ligand complex during simultaneous photolyses of Cu(II)(Et2dtc)+ and Cu(II)(Et2dtc)2 species in toluene/ROH. The role of the solvent is discussed from the combined analysis of spectrophotometric and EPR data and quantum yield results.     

Correlation between i.r. spectra and thermal decomposition of cobalt(II), nickel(II), copper(II) and mercury(II) complexes with piperidinedithiocarbamate and pyrrolidinedithiocarbamate

The thermal decomposition of pyrrolidinedithiocarbamate and piperidinedithiocarbamate complexes of Co^II, Ni^II, Cu^II and Hg^II have been studied by thermogravimetry and differential scanning calorimetry. The decomposition intermediates and final products were identified by their X-ray diffraction patterns. The i.r. spectra are discussed in terms of the thermal decomposition pathways.