Versatile nuclearity in copper complexes with ortho functionalized 1,3-bis(aryl)triazenido ligands

The synthesis, characterization and crystal structures of three new copper complexes derived from 1,3-bis(aryl)triazenido ligands bearing either a methoxycarbonyl, methylthio or a hydroxymethyl group in the ortho position of one of the aromatic rings are reported. In addition to the coordination of the triazenido fragment, the Lewis basic groups coordinate to the copper centers to form complexes with different nuclearity: {1-[2-(methoxycarbonyl)phenyl]-3-[4-methylphenyl]}triazene and {1-[2-(methylthio)phenyl]-3-[4-methylphenyl]}triazene form stable dinuclear and tetranuclear Cu(I) complexes, respectively. Reaction of {1-[2-(hydroxymethyl)phenyl]-3-[4-methylphenyl]}triazene with either Cu(I) or Cu(II) results in a novel Cu(II) hexanuclear macrocyclic complex.     

Reversibility of the effects of cadmium on the growth and nitrogen metabolism in the tomato(Lycopersicon esculentum)

In order to better understand the effects of heavy metals on the growth of plants, we decided to perform recovering experiments by following both chemical and physiological parameters in cadmium pre-stressed tomato seedlings after cadmium had been removed from the nutrient solution. The work shows that cadmium suppression results in resumption of growth activity. The biomass of leaves and stems rose steadily. The increase in root biomass exceeded those of leaves and stems. At the same time, nitrate content was increased to reach the level obtained with unstressed controls. In all the organs studied, the activities of the enzymes involved in the anabolic nitrogen primary assimilation pathways (nitrate reductase (NR), nitrite reductase (NiR) and glutamine synthetase (GS) soared after that cadmium had been removed. While NAD(+)-dependent glutamate dehydrogenase (GDH-NAD+) activity also rose progressively during the recovering time, the cognate NADH-dependent glutamate dehydrogenase (GDH-NADH) activity decreased. This result allows us to propose that the ammonia produced by the stress-induced protein catabolism is detoxified and re-assimilated by the GDH-NADH isoenzyme. On the basis of these results, we will discuss the ability of the plant to dilute the effects of pollutants during the recovering period. An important outcome of this work is that a transient contamination of the culture medium by pollutants is not necessarily followed by a significant depreciation in product yield or quality.     

Preparation, structural, magnetic and thermal properties of two heterobimetallic cyano-bridged nickel(II)-copper(II)/platinum(II) coordination polymers

Two unique bimetalic Pt(II) coordination polymers of composition [Ni(hydeten)₂Pt(CN)₄] (Ni-Pt) and [Cu(hydeten)₂Pt(CN)₄] (Cu-Pt) [hydeten = N-(2-hydroxyethyl-ethylenediamine) or 2-(2-aminoethylamino)ethanol] have been synthesized and structurally characterized by various methods in this study. The crystal structure of Cu-Pt was determined by single-crystal X-ray diffraction analysis. The structure of Cu-Pt forms of infinite 2,2-TT type [-Cu(hydeten)₂-NC-Pt(CN)₂-CN-] chains containing paramagnetic copper atoms bridged by tetracyanoplatinate species. In this complex, Cu(II) centers display an axially elongated octahedron with two chelating hydeten molecules in the equatorial positions and N-bonded bridging cyano groups in the axial positions, whereas Pt(II) centers are four coordinate with four cyanide-carbon atoms in a square-planar arrangement. The decrease of the moments of these complexes in temperature range of 50 305 K can assigned to the antiferromagnetic interactions in the structures. The thermal decomposition of Cu-Pt comprise of five distinguished stages, while the thermal decomposition of Ni-Pt take place four different stages.     

Transition metal-saccharide chemistry: d-glucose complexes of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)

Metal complexes of d-glucose (d-Glc) from large cation containing dibromo-dichloro salts of dipositive metals [NEt₄]₂[MBr₂Cl₂] (M = Mn, Co, Ni, Cu and Zn) and the disodium salt of glucose were synthesized from a MeOH:MeCN mixture. The complexes were characterized by UV-vis absorption, circular dichroism, IR and proton magnetic resonance spectroscopies, and by elemental analysis, and were found to be Na[M(d-Glc)(OMe)Cl]. Cyclic voltammetric studies of these complexes, in the acidic to neutral pH range, indicated no dissociation, even in highly acidic conditions.This paper is dedicated to Professor Richard H. Holm (Harvard University) on the occasion of his 60th birthday.     

Homoleptic copper(II) and copper(I) complexes of 5,6-dihydro-5,6-epoxy-1,10-phenanthroline. Six-coordinate copper(I) in solution

Reaction of 5,6-dihydro-5,6-epoxy-1,10-phenanthroline (L) with Cu(ClO₄)₂·6H₂O in methanol in 3:1 M ratio at room temperature yields light green [CuL₃](ClO₄)₂·H₂O (1). The X-ray crystal structure of the hemi acetonitrile solvate [CuL₃](ClO₄)₂·0.5CH₃CN has been determined which shows Jahn-Teller distortion in the CuN₆ core present in the cation [CuL₃]²⁺. Complex 1 gives an axial EPR spectrum in acetonitrile-toluene glass with g_|| = 2.262 (A_|| = 169 × 10⁻⁴ cm⁻¹) and g_⊥ = 2.069. The Cu(II/I) potential in 1 in CH₂Cl₂ at a glassy carbon electrode is 0.32 V versus NHE. This potential does not change with the addition of extra L in the medium implicating generation of a six-coordinate copper(I) species [CuL₃]⁺ in solution. B3LYP/LanL2DZ calculations show that the six Cu-N bond distances in [CuL₃]⁺ are 2.33, 2.25, 2.32, 2.25, 2.28 and 2.25 Å while the ideal Cu(I)-N bond length in a symmetric Cu(I)N₆ moiety is estimated as 2.25 Å. Reaction of L with Cu(CH₃CN)₄ClO₄ in dehydrated methanol at room temperature even in 4:1 M proportion yields [CuL₂]ClO₄ (2). Its ¹H NMR spectrum indicates that the metal in [CuL₂]⁺ is tetrahedral. The Cu(II/I) potential in 2 is found to be 0.68 V versus NHE in CH₂Cl₂ at a glassy carbon electrode. In presence of excess L, 2 yields the cyclic voltammogram of 1. From ¹H NMR titration, the free energy of binding of L to [CuL₂]⁺ to produce [CuL₃]⁺ in CD₂Cl₂ at 298 K is estimated as −11.7 (±0.2) kJ mol⁻¹.     

Heterometallic Ni/Zn amine complexes possessing extended 2D and 3D hydrogen-bonded networks prepared from zinc oxide

Five novel heterometallic Ni/Zn coordination compounds [Ni(en)₃][ZnCl₄] (1), [Ni(en)(Hea)₂][ZnCl₄] (2), [Ni(dien)₂][ZnCl₄] (3), [Ni(en)₃][ZnCl₄] · 2DMSO (4) and [Ni(en)₃][Zn(NCS)₄] · CH₃CN (5), where en = ethylenediamine (ethane-1,2-diamine), Hea = monoethanolamine (2-aminoethanol) and dien = diethylenetriamine (1,4,7-triazaheptane), have been synthesized by means of the open-air reaction of zinc oxide, nickel chloride (or nickel powder), NH₄X (X = Cl, NCS) and ligand (en, dien, Hea) in non-aqueous solvents, such as DMSO, DMF, CH₃OH and CH₃CN. The choice of a counter-anion in the initial ammonium salt as well as selection of the ligand and solvent provides an effortless approach to the controlled assembly of two- or three-dimensional extended networks assisted by hydrogen bonding. Crystallographic investigations reveal that 1, 2 and 5 possess 3D, while 3 and 4 exhibit 2D H-bonded crystal structures. The structures of the compounds exhibit six-coordinated Ni(II) centers and four-coordinated Zn(II) centers in distorted octahedral and tetrahedral geometries, respectively.     

Can nucleotides prevent Cu-induced oxidative damage?

Cu-induced oxidative damage is associated with cancer, diabetes, neurodegenerative and age related diseases. The quest for Cu-chelators as potential antioxidants spans the past decades. Yet, biocompatible Cu-chelators that do not alter the normal metal-ion homeostasis are still lacking. Here, we explored the potential of natural and synthetic nucleotides and inorganic phosphates as inhibitors of the Cu(I)/(II)-induced ()OH formation via either the Fenton or Haber-Weiss mechanisms. For this purpose, we studied by ESR the modulation of Cu-induced ()OH production, from the decomposition of H(2)O(2), by nucleotides and phosphates. ATP inhibited both Cu(I) and Cu(II) catalyzed reactions (IC(50) 0.11 and 0.04mM, respectively). Likewise, adenosine 5'-beta,gamma-methylene triphosphate (AMP-PCP), adenosine 5'-O-(3-thiotriphosphate) (ATP-gamma-S), ADP and tripolyphosphate were identified as good inhibitors. However, AMP and adenosine were poor inhibitors in the Cu(I)-H(2)O(2) system, IC(50) ca. 1.2mM, and radical enhancers in the Cu(II)-H(2)O(2) system. The best antioxidant was adenosine 5'-[beta,gamma-imino] triphosphate (AMP-PNP) (IC(50) 0.05mM at Cu(I)-H(2)O(2) system) which was 15 times more active than the known antioxidant Trolox. ATP and analogues inhibit Cu-induced ()OH formation through an ion chelation rather than a scavenging mechanism. Two phosphate groups are required for making active Fenton-reaction inhibitors. Nucleotides and phosphates triggered a biphasic modulation of the Haber-Weiss reaction, but a monophasic inhibition of the Fenton reaction. We conclude that nucleotides at sub mM concentrations can prevent Cu-induced OH radical formation from H(2)O(2), and hence may possibly prevent oxidative damage.     

The role of terminal amino group and histidine at the fourth position in the metal ion binding of oligopeptides revisited: Copper(II) and nickel(II) complexes of glycyl-glycyl-glycyl-histamine and its N-Boc protected derivative

Copper(II) and nickel(II) binding properties of two pseudo tetrapeptides, N-Boc-Gly-Gly-Gly-Histamine (BGGGHa) and Gly-Gly-Gly-Histamine (GGGHa) have been investigated by pH-potentiometric titrations, UV-visible-, EPR-, NMR- and ESI-HRMS (electrospray ionization high resolution MS) spectroscopies, in order to compare the role of N-terminal amino group and imidazole moiety at the fourth position in the complex formation processes. Substantially higher stabilities were determined for the ML complexes of GGGHa, compared to those of BGGGHa, supporting the coordination of the terminal amino group and the histamine imidazole of the non-protected ligand. A dimeric Cu₂H_− 2L₂ species, formed through the deprotonation of peptide groups of the ligands, was found in the GGGHa-copper(II) system. Deprotonation and coordination of further amide nitrogens led to CuH_− 2L and, above pH ~ 10, CuH_− 3L. Experimental data supports a {NH₂,2 × N_amide,N_im} macrochelate structure in CuH_− 2L whereas a {NH₂,3 × N_amide} coordination environment in CuH_− 3L. The first two amide deprotonation processes were found to be strongly cooperative with nickel(II) and spectroscopic studies proved the transformation of the octahedral parent complexes to square planar, yellow, diamagnetic species, NiH_− 2L and above pH ~ 9, NiH_− 3L. In the basic pH-range deprotonation and coordination of the amide groups also took place in the BGGGHa containing systems, leading to complexes with a {3 × N_amide,N_im} donor set, and in parallel the re-dissolving of precipitate. Above pH ~ 11, a further proton release from the pyrrolic NH group of the imidazole ring of BGGGHa occurred providing an additional proof for the different binding modes of the two ligands.     

Copper and zinc binding properties of the N-terminal histidine-rich sequence of Haemophilus ducreyi Cu,Zn superoxide dismutase

The Cu,Zn superoxide dismutase (Cu,ZnSOD) isolated from Haemophilus ducreyi possesses a His-rich N-terminal metal binding domain, which has been previously proposed to play a copper(II) chaperoning role. To analyze the metal binding ability and selectivity of the histidine-rich domain we have carried out thermodynamic and solution structural analysis of the copper(II) and zinc(II) complexes of a peptide corresponding to the first 11 amino acids of the enzyme (H₂N-HGDHMHNHDTK-OH, L). This peptide has highly versatile metal binding ability and provides one and three high affinity binding sites for zinc(II) and copper(II), respectively. In equimolar solutions the MHL complexes are dominant in the neutral pH-range with protonated lysine ε-amino group. As a consequence of its multidentate nature, L binds zinc and copper with extraordinary high affinity (K_D,Zn = 1.6 × 10⁻⁹ M and K_D,Cu = 5.0 × 10⁻¹² M at pH 7.4) and appears as the strongest zinc(II) and copper(II) chelator between the His-rich peptides so far investigated. These K_D values support the already proposed role of the N-terminal His-rich region of H. ducreyi Cu,ZnSOD in copper recruitment under metal starvation, and indicate a similar function in the zinc(II) uptake, too. The kinetics of copper(II) transfer from L to the active site of Cu-free N-deleted H. ducreyi Cu,ZnSOD showed significant pH and copper-to-peptide ratio dependence, indicating specific structural requirements during the metal ion transfer to the active site. Interestingly, the complex CuHL has significant superoxide dismutase like activity, which may suggest multifunctional role of the copper(II)-bound N-terminal His-rich domain of H. ducreyi Cu,ZnSOD.     

New metal complexes with 5-(1H-imidazol-4-ylmethyl)aminoisophthalic acid: Syntheses, structures, electrochemistry and electrocatalysis

Three new coordination polymers {[Cu(HL)(H₂O)]·H₂O}_n (1), [Ag(H₂L)]_n (2), and {[Co(HL)(phen)(H₂O)]·8H₂O}_n (3) [H₃L = 5-(1H-imidazol-4-ylmethyl)aminoisophthalic acid, phen = 1,10-phenanthroline] have been synthesized under hydrothermal conditions. The results of X-ray diffraction analysis revealed that complex 1 displays (3, 3)-connected 2D network with (4, 8²) topology, while complexes 2 and 3 have infinite 1D chain structure, in which one of the two carboxylic groups of H₂L⁻/HL²⁻ is uncoordinated. The 2D layers of 1 or the 1D chains of 2 and 3 are further linked together by hydrogen bonds and π-π interactions to form 3D supramolecular frameworks. Moreover, the electrochemical properties of complexes 1 and 2 have been studied by modified glassy carbon electrodes of 1 (Cu-GCE) and 2 (Ag-GCE), and the results indicate that the Cu-GCE and Ag-GCE show one-electron redox peaks. In addition, both Cu-GCE and Ag-GCE have good electrocatalytic activities toward the reduction of H₂O₂ in phosphate buffer (pH 5.5) solution.     

Metal-binding ability of histidine-containing peptidehydroxamic acids: Imidazole versus hydroxamate coordination

Three new peptidehydroxamic acids (l-alanyl-l-histidinehydroxamic acid, l-Ala-l-HisNHOH, l-alanyl-l-alanyl-l-histidinehydroxamic acid, l-Ala-l-Ala-l-HisNHOH and l-histidyl-l-alaninehydroxamic acid, l-His-l-AlaNHOH) were synthesized and their complexation with Cu(II), Ni(II) and Zn(II) were studied by pH-potentiometric, UV-Vis, CD, ¹H NMR, EPR and ESI-MS methods. Each of the studied peptide derivatives involves one side-chain imidazole unit and the effect of this group on the metal binding of the hydroxamic moiety is evaluated in the paper. The obtained results are compared to those of the complexes of some histidine-containing di- or tripeptides and also to those of hydroxamic derivatives of aliphatic peptides.A competition between the hydroxamate and imidazole functions occurs in all systems, but the extent differs from metal to metal, from ligand to ligand and depends very much on the pH. The imidazole was found to play the most determinant role in the Cu(II) complexes, somewhat less in the Ni(II)-containing ones, while (except the case of l-Ala-l-HisNHOH) negligible role was found in the Zn(II)-complexes. Common feature of the Ni(II)- and especially Cu(II)-containing systems is that if an imidazole-N is displaced by a hydroxamate, imidazole-bridged di- and polynuclear complexes are formed.     

Highly symmetrical chromium(II) bisdiketiminate complexes

Reaction of the lithium salts of N,N′-dialkyl-2-amino-4-imino-pent-2-enes, nacnac^RLi(THF) (R = CH₂Ph, Cy, nPr, iBu or S-CH(Me)Ph), with half an equivalent of CrCl₂(THF)_x yielded the homoleptic complexes (nacnac^R)₂Cr. All complexes were characterized by X-ray diffraction studies and displayed a highly symmetric, square-planar coordination around the chromium center with strong boat-like distortions of the diketiminate ligands. Reaction of nacnac^RLi(THF) (R = CH₂Ph, Cy) with one equivalent of CrCl₂(THF)_x afforded the dimeric complexes {nacnac^RCr(μ-Cl)}₂.     

Reactivity of trans-[PtCl2(NCMe)2] with cycloaliphatic amines: An ESI and NMR study. X-ray structure of

The reactivity of the cyclic primary aliphatic amines cyclopropyl-, cyclopentyl- and cyclohexylamine with cis- and trans-[PtCl₂(NCMe)₂], under the same experimental conditions, is compared. Whereas cis-[PtCl₂(NCMe)₂] yields the neutral diamidine compounds, the reactions with trans-[PtCl₂(NCMe)₂] take place either with addition or substitution processes yielding the neutral diamidine complexes trans-[PtCl₂(Amidine)₂], the monocationic trans-[PtCl(Amine)(Amidine)₂]Cl and the dicationic trans-[Pt(Amine)₂(Amidine)₂]Cl₂ salts. An NMR and ESI study indicate that the main species formed is the monocationic trans-[PtCl(Amine)(Amidine)₂]Cl complex.The X-ray structure of is reported and its supramolecular arrangement is described.     

Polynuclear nickel (II) and copper (II) complexes of hexaazamacrocycles incorporating pairs of diethylenetriamine subunits separated by aromatic spacers

A series of Ni(II) and Cu(II) complexes of the hexaaza macrocycles, 3,6,9,17,20,23-hexaazatricyclo[23.3.1.1^11,15]triaconta-1(29),11(30),12,14,25,27-hexaene (L¹) and 3,6,9,16,19,22-hexaazatricyclo[22.2.2.2^11,14]triaconta-1(26),11(29),12,14(30),24(28),25-hexaene (L²), have been prepared and the crystal structures determined for [Ni₂L¹(O₂CCH₃)₂(H₂O)₂](ClO₄)₂ (1), [Ni₂L²(DMF)₆](ClO₄)₄ · 2H₂O (2), {[Cu₂L²Br(O₂CCH₃)](ClO₄)₂}_n (3), [Cu₂L²(μ-CO₃)(H₂O)₂]₂(ClO₄)₄ · 8H₂O (4), [Cu₂L²(O₂CCH₃)₂](BF₄)₂ (5), and [Cu₂L¹(μ-imidazolate)Br]₂Br₄ · 6H₂O (6). In these complexes, two metal centers are bound per ligand; in 1 and 3-6, the N₃ subunits of L¹ or L² coordinate meridionally to the metal centers, whilst in 2, each N₃ subunit in L² adopts a facial mode of coordination. The binuclear cations in 1 and 2 have chair-like conformations, with the distorted octahedral Ni(II) coordination spheres completed by terminal water and a bidentate acetate ligand in 1 and three DMF ligands in 2. The Cu(II) centers in 3-6 generally reside in square planar environments, although a weakly binding ligand enters the coordination sphere in some cases, generating a distorted square pyramidal geometry. The binuclear [Cu₂L²]⁴⁺ units in 3, 4 and 5 adopt similar bowl-shaped conformations, stabilized by H-bonding interactions between pairs of amine groups from L² and a perchlorate or tetrafluoroborate anion. In 3, the binuclear units are linked through acetate groups, bridging in a syn-anti fashion, to produce a zig-zag polymeric chain structure, whilst 4 incorporates a tetrameric cation consisting of two binuclear units linked via a pair of carbonate bridges. Compound 6 features an imidazolate bridge between the two Cu(II) centers bound by L¹. Pairs of [Cu₂L¹(μ-imidazolate)]³⁺ units are then weakly linked through a pair of bromide anions.     

On the possible roles of N-terminal His-rich domains of Cu,Zn SODs of some Gram-negative bacteria

The Cu,Zn superoxide dismutases (Cu,Zn SOD) isolated from some Gram-negative bacteria possess a His-rich N-terminal metal binding extension. The N-terminal domain of Haemophilus ducreyi Cu,Zn SOD has been previously proposed to play a copper(II)-, and may be a zinc(II)-chaperoning role under metal ion starvation, and to behave as a temporary (low activity) superoxide dismutating center if copper(II) is available. The N-terminal extension of Cu,Zn SOD from Actinobacillus pleuropneumoniae starts with an analogous sequence (HxDHxH), but contains considerably fewer metal binding sites. In order to study the possibility of the generalization of the above mentioned functions over all Gram-negative bacteria possessing His-rich N-terminal extension, here we report thermodynamic and solution structural analysis of the copper(II) and zinc(II) complexes of a peptide corresponding to the first eight amino acids (HADHDHKK-NH₂, L) of the enzyme isolated from A. pleuropneumoniae. In equimolar solutions of Cu(II)/Zn(II) and the peptide the MH₂L complexes are dominant in the neutral pH-range. L has extraordinary copper(II) sequestering capacity (K_D,Cu = 7.4 × 10^− 13 M at pH 7.4), which is provided only by non-amide (side chain) donors. The central ion in CuH₂L is coordinated by four nitrogens {NH₂,3N_im} in the equatorial plane. In ZnH₂L the peptide binds to zinc(II) through a {NH₂,2N_im,COO⁻} donor set, and its zinc binding affinity is relatively modest (K_D,Zn = 4.8 × 10^− 7 M at pH 7.4). Consequently, the presented data do support a general chaperoning role of the N-terminal His-rich region of Gram-negative bacteria in copper(II) uptake, but do not confirm similar function for zinc(II). Interestingly, the complex CuH₂L has very high SOD-like activity, which may further support the multifunctional role of the copper(II)-bound N-terminal His-rich domain of Cu,Zn SODs of Gram-negative bacteria. The proposed structure for the MH₂L complexes has been verified by semiempirical quantum chemical calculations (PM6), too.     

A zinc-finger like metal binding site in the nucleosome

UV spectroscopy demonstrated that chicken mononucleosomes bind Co(II) and Zn(II) ions at submicromolar concentrations in a tetrahedral mode, at a conserved zinc finger-like site, composed of Cys110 and His113 residues of both H3 molecules. Neither of these metal ions substituted for another, indicating a limited binding reversibility. Molecular modeling indicated that the tetrahedral site is formed by unhindered rotations around Calpha-Cbeta bonds in the side chains of the zinc binding residues. The resulting local rearrangement of the protein structure shields the bound metal ion from the solvent, explaining the observed lack of reversibility of the binding. Consequences of these findings for zinc homeostasis, metal toxicology and nucleosomal regulation are discussed.     

Synthesis and characterization of alkynes β-diketonate copper(I) complexes

The reactions of 1,3,5-tris-(trimethylsilylethynyl)benzene (1) with Cu₂O and 1,1,1,5,5,5,-hexafluoroacetylacetone in alkyne to Cu ratios 1:0.5, 1:1 and 1:3 in CH₂Cl₂ at room temperature give copper complexes (η²-1,3,5-tris(trimethylsilylethynyl)benzene)(Cu(hfac)) (2), (η²:η²-1,3,5-tris(trimethylsilylethynyl)benzene)(Cu(hfac))₂ (3) and (η²:η²:η²-(1,3,5- tris(trimethylsilylethynyl)benzene))₂(Cu(hfac))₃(4), respectively. In the same conditions, 2,5-bis-(trimethylsilylethynyl)thiophene (5) reacts with 0.5 or 1 equiv. of Cu₂O to give (η²:η²-2,5-bis(trimethylsilylethynyl)thiophene)(Cu(hfac)) (6) and (η²:η²-2,5-bis(trimethylsilylethynyl)thiophene)(Cu(hfac))₂ (7), respectively, and 1,4-bis(trimethylsilyl)-1,3-butadiyne (8) with 0.5 equiv. of Cu₂O give (η²:η²-1,4-bis(trimethylsilyl)-1,3-butadiyne)(Cu(hfac))₂(9). All the new compounds have been characterized by analytical and spectroscopic methods and their thermal properties were examined by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC).     

Synthesis, structural determination and magnetic properties of a heterobimetallic CuRe complex containing a macrocyclic ligand

Reaction of the rhenium(IV) compound, [Bu₄N]₂ReCl₄ox, with the highly unsaturated tetraazabismacrocyclic copper(II) complex cation [CuCuL]⁴⁺ (L = 6,13-Bis(dodecylaminomethylidene)-1,4,8,11-tetraazacyclotetradeca-4,7,11,14-tetraene) produced a new kind of heterobimetallic compound: [CuCuL][ReCl₄ox]₂ · 2DMF in which [ReCl₄ox]²⁻ anions and [CuCuL]⁴⁺ cations are linked by electrostatic forces. The crystal structure of this compound was determined at 173(2) K. It crystallizes triclinic, space group , with a = 9.441(4), b = 11.032(5), c = 15.261(7) Å, α = 89.05(1)°, β = 88.93(1)°, γ = 77.09(1)°, Z = 1, R₁ = 0.0557, wR₂ = 0.1332. The magnetic behavior of this compound has been investigated over the temperature range 1.72-300 K. The compound behaves as a ferrimagnetic Cu^IIRe^IV bimetallic, chain with intrachain antiferromagnetic coupling.     

Imidazole derivatives of binuclear copper (II) and nickel (II) complexes incorporating bis(1,4,7-triazacyclononan-1-yl) ligands

A series of new binuclear copper (II) and nickel (II) complexes of the macrocyclic ligands bis(1,4,7-triazacyclononan-1-yl)butane (L^but) and bis(1,4,7-triazacyclononan-1-yl)-m-xylene (L^mx) have been synthesized: [Cu₂L^butBr₄] (1), [Cu₂L^but(imidazole)₂Br₂](ClO₄)₂ (2), [Cu₂L^mx(μ-OH)(imidazole)₂](ClO₄)₃ (3), [Cu₂L^but(imidazole)₄](ClO₄)₄ · H₂O (4), [Cu₂L^mx(imidazole)₄](ClO₄)₄ (5), [Ni₂ L^but(H₂O)₆](ClO₄)₄ · 2H₂O (6), [Ni₂L^but(imidazole)₆](ClO₄)₄ · 2H₂O (7) and [Ni₂L^mx (imidazole)₄(H₂O)₂](ClO₄)₄ · 3H₂O (8). Complexes 1, 2, 7 and 8 have been characterized by single crystal X-ray studies. In each of the complexes, the two tridentate 1,4,7-triazacyclononane rings of the ligand facially coordinate to separate metal centres. The distorted square-pyramidal coordination sphere of the copper (II) centres is completed by bromide anions in the case of 1 and/or monodentate imidazole ligands in complexes 2, 4 and 5. Complex 3 has been formulated as a monohydroxo-bridged complex featuring two terminal imidazole ligands. Complexes 6-8 feature distorted octahedral nickel (II) centres with water and/or monodentate imidazole ligands occupying the remaining coordination sites. Within the crystal structures, the ligands adopt trans conformations, with the two metal binding compartments widely separated, perhaps as a consequence of electrostatic repulsion between the cationic metal centres. The imidazole-bearing complexes may be viewed as simple models for the coordinative interaction of the binuclear complexes of bis (tacn) ligands with protein molecules bearing multiple surface-exposed histidine residues.     

Synthesis and chemical characterization of Cu, Ni and Zn complexes of 3,5-bis(2′-pyridyl)-1,2,4-oxadiazole and 3-(2′-pyridyl)5-(phenyl)-1,2,4-oxadiazole ligands

The synthesis and structural characterization of Ni^II, Cu^II and Zn^II complexes of two chelating 1,2,4-oxadiazole ligands, namely 3,5-bis(2′-pyridyl)-1,2,4-oxadiazole (bipyOXA) and 3-(2′-pyridyl)5-(phenyl)-1,2,4-oxadiazole (pyOXA), is here reported. The formed hexacoordinated metal complexes are [M(bipyOXA)₂(H₂O)₂](ClO₄)₂ and [M(pyOXA)₂(ClO₄)₂], respectively (M = Ni, Cu, Zn). X-ray crystallography, ¹H and ¹³C NMR spectroscopy and C, N, H elemental analysis data concord in attributing them an octahedral coordination geometry. The two coordinated pyOXA ligands assume a trans coplanar disposition, while the two bipyOXA ligands are not. The latter result is a possible consequence of the formation of H-bonds between the coordinated water molecules and the nitrogen atom of the pyridine in position 5 of the oxadiazole ring. The expected splitting of the d metal orbitals in an octahedral ligand field explains the observed paramagnetism of the d⁸ and d⁹ electron configuration of the nickel(II) and copper(II) complexes, respectively, as determined by the broadening of their NMR spectra.