Cuprous complexes and dioxygen. Part X. Influence of ring size on the autoxidation of Cu(I) complexes with cis-and trans-N2S2 macrocyclic ligands

The autoxidation of the Cu⁺ complexes with a series of six 12-, 14- and 16-membered macrocycles containing the N₂S₂ set of donor atoms has been studied with an oxygen electrode and with the stopped-flow technique. Inspite of the identical set of coordinating groups, the reactivity of the Cu⁼ complexes towards O₂ varies by more than 5 orders of magnitude, with rate constants between <0.1 and 2·10⁴ M^?1S^?1. Simple bimolecular rate laws are obtained from initial rates of autoxidation, but successive one-electron transfers with intermediate formation of superoxide are implied from the analysis of complete reaction curves for complexes with the 12-membered macrocycles. The kinetic parameters are compared with the redox potentials for the corresponding CuL²⁺/CuL⁺ couples. Only a rather rough correlation is found and steric factors must in addition be responsible for the observed reactivity pattern which shows a decrease of autoxidation rate with increasing size of the macrocyclic ring. No systematic effect was observed for the influence of cis- vs. trans-configuration of the donor atoms.     

Synthesis,characterization and antimicrobial activity of 5‐(arylazo)salicylaldimines and their copper(II) complexes

A new series of twelve bidentate Schiff's base ligands (HL^1–12) was synthesized via condensation of 5‐(arylazo)salicylaldehydes with aromatic amines. When the new salicylaldimine derivatives were reacted with copper(II) chloride, the neutral complexes Cu(L^1–12)₂ were obtained. The structure of the copper complexes was established from microanalyses, IR and UV spectra and thermal analyses. The results suggested that the ligands were coordinated to the metal ion in a bidentate manner with ON donor sites of the deprotonated phenolic‐OH and azomethine‐N. The composition of the complexes can be represented as CuL₂. Evaluation of antimicrobial activity for the synthesized compounds was carried out to probe their activity. The compounds were found to have weak antimicrobial activity.     

POTENTIOMETRIC,POLAROGRAPHIC AND SPECTROSCOPIC STUDIES OF THE Cu(II)-D-GLUCOSAMINE-D-LACTOBIONIC ACID TERNARY SYSTEMS

Abstract

Our recent work on Cu(II) and VO(IV) interactions with lactobionic acid have shown^1,2 that this sugar acid has an unusually high ability to coordinate both metal ions. The carboxyl group is not a very effective donor for cupric ions^3,4 and metal interations with the set of the protonated hydroxyl groups should have considerable effects on complex stability. This high stability of the lactobionic acid complexes can lead to the involvement of this ligand in formation of ternary complexes with ligands such as aminosugars.^3–6 Both ligands are important chelating agents for Cu(II) ions in medicine, agriculture and food chemistry.^7–9 Since ternary complexes may play an important role in natural systems we have decided to follow complex formation in solutions containing lactobionic acid and one an aminosugar, D-glucosamine. The anchoring group in D(+)-glucosamine (2-amino-2-deoxy-D-glucose) is an amino group which is much more effective donor than carboxylate which acts as an anchor in sugar acids. Thus in our study we have used excess lactobionic acid to promote the formation of ternary complexes as major species in the solutions studied.     

Synthesis,characterization, and antioxidant activities of three Cu(II) complexes with Schiff-base ligands

Cu(II) complexes of three bis(pyrrol-2-yl-methyleneamine) ligands were synthesized and characterized by elemental analyses, mass spectra, and IR spectra. X-ray diffraction analysis shows that [CuL³]₂ is a dinuclear complex with an extremely distorted square-planar geometry. Furthermore, the antioxidant activities of the compounds have been investigated. The electrochemical properties of the Cu(II) complexes have also been studied by cyclic voltammetry. The Cu(II) complexes show similar superoxide dismutase (SOD) activity compared with that of the native Cu, Zn-SOD.     

Square planar complexes of Cu(II) and Ni(II) with N<Subscript>2</Subscript>O donor set of two Schiff base ligands: synthesis and structural aspects

Abstract Two new square planar Cu(II) and Ni(II) complexes, [CuL¹(NCO)] (1) and [NiL²(N₃)] (2) have been synthesized with two different tridentate N₂O donor Schiff base ligands L ¹ H (1:1 condensation product of benzoylacetone and 2-diethylaminoethylamine) and L ² H (1:1 condensation product of benzoylacetone and 2-dimethylaminoethylamine), respectively. Both the complexes 1 and 2 have been characterized by elemental analysis, IR, UV-Vis spectroscopy, room temperature magnetic susceptibility measurement, electrochemical, thermal, and single crystal X-ray diffraction studies. Structural studies reveal that in both the complexes metal centers have square planar environment with N₂O donor set of Schiff base ligands and terminal pseudohalide anions (isocyanate for 1 and azide for 2) at four coordination sites of square plane. Graphical abstract Square planar complexes of Cu(II) and Ni(II) with N ₂ O donor set of two Schiff base ligands: synthesis and structural aspects Subhra Basak, Soma Sen, Samiran Mitra, C. Marschner, W. S. Sheldrick Two new square planar Cu(II) and Ni(II) complexes, [CuL¹(NCO)] (1) and [NiL²(N₃)] (2) have been synthesized with two different tridentate N₂O donor Schiff base ligands L ¹ H and L ² H respectively. Both the complexes 1 and 2 have been characterized by elemental analysis, IR, UV-Vis spectroscopy, room temperature magnetic susceptibility measurement, electrochemical, thermal and single crystal X-ray diffraction studies.      

Studies of Electrode Reactions and Coordination Geometries of Cu(I) and Cu(II) Complexes with Bicinchoninic Acid

Bicinchoninic acid (BCA) is widely used for determining the valence state of copper in biological systems and quantification of the total protein concentration (BCA assay). Despite its well‐known high selectivity of Cu(I) over Cu(II), the exact formation constants for Cu(I)(BCA)₂³⁻ and Cu(II)(BCA)₂²⁻ complexes remain uncertain. These uncertainties, affect the correct interpretations of the roles of copper in biological processes and the BCA assay data. By studying the voltammetric behaviors of Cu(I)(BCA)₂³⁻ and Cu(II)(BCA)₂²⁻, we demonstrate that the apparent lack of redox reaction reversibility is caused by an adsorption wave of Cu(II)(BCA)₂²⁻. With the adsorption wave identified, we found that the Cu(I)/Cu(II) selectivity of BCA is essentially identical to another popular ligand, bathocuproinedisulfonic acid (BCS). Density functional theory calculation on the geometries of Cu(I)(BCA)₂³⁻ and Cu(II)(BCA)₂²⁻ rationalizes the preferential Cu(I) binding by BCA and the strong adsorption of the Cu(II)(BCA)₂²⁻ complex at the glassy carbon electrode. Based on the shift in the standard reduction potential of free Cu(II)/Cu(I) upon binding to BCA, we affirm that the formation constants for Cu(I)(BCA)₂³⁻ and Cu(II)(BCA)₂²⁻ are 10^17.2 and 10^8.9, respectively. Therefore, BCA can be chosen among various ligands for effective and reliable studies of the copper binding affinities of different biomolecules.     

The effect of 2,2′-bipyridyl on the stability of Cu(II) complexes with carboxylic acids

The stability constants β₂, and β₂ of simple Cu(II) complexes with methoxyacetic, phenylacetic, and cyclohexylacetic acid were determined spectrophotometrically and compared with the stability of composite complexes containing 2,2′-bipyridyl as the first ligand and the above mentioned acid as the second ligand. In each case the stability of the composite complex Cu(bip)L⁺ was found to exceed that of the simple complex CuL⁺ and the differences in the values of log β are comprised within 0.15–0.17.     

Comparison of the Complexation of Open-Chain and Cyclic N2S2 Ligands with Cu+ and Cu2+

The complexation properties of the open-chain N₂S₂ ligands 1–4 are described and compared to those of analogous N₂S₂ macrocycles 5–7 . With Cu²⁺, the open-chain ligands give complexes with the stoichiometry CuL²⁺ and CuLOH⁺, the stabilities and absorption spectra of which have been determined. The ligand field exerted by these ligands is relatively constant and independent of the length of the chain. With Cu⁺, the species CuLH, CuLH²⁺, and CuL⁺ were identified and their stabilities measured. The redox potentials calculated from the equilibrium constants and measured by cyclic voltammetry agree and lie between 250 and 280 mV against SHE. The comparison between open-chain and cyclic ligands shows that (1) a macrocyclic effect is found for Cu²⁺ but not for Cu⁺, (2) the ligand-field strength is very different for the two types of ligands, and (3) the redox potentials span a larger interval for the macrocyclic than for the open-chain complexes.     

The relationship between the electrospray ionization behaviour and biological activity of some phosphino Cu(I) complexes

Electrospray ionization mass spectrometry was usefully employed for the characterization of three phosphino copper(I) complexes of medicinal interest. This technique revealed that the original [CuL₄]⁺ pro‐drugs (L = hydrophilic tertiary phosphine) underwent dissociation with production of coordinative unsaturated [CuL₃]⁺ and [CuL₂]⁺ species, which represented key intermediates for the activation of potential biological properties. The more favoured was the displacement of the ligands from the [CuL₄]⁺ parent complex, the more favoured was in turn the possibility for the metal ion to directly interact with biological substrates, including pharmacological targets related to cancer proliferation. An inverse correlation between the stability and the cytotoxic activity of the three copper(I) complexes investigated has been clearly established. Copyright © 2010 John Wiley & Sons, Ltd.     

Antimicrobial,antioxidant and SOD activities of copper(II) complexes derived from 2-aminobenzothiazole derivatives

A series of Cu(II) complexes have been synthesized from bidentate Schiff base ligands (by condensation of Knoevenagel condensate of acetoacetanilide (obtained from substituted benzaldehydes and acetoacetanilide) and 2-aminobenzothiazole). They were characterized by elemental analysis, IR, ¹H NMR, ¹³C NMR, UV–vis., molar conductance, magnetic moment, ESR spectra and electrochemical studies. Based on the magnetic moment, ESR, and electronic spectral data, a distorted square planar geometry has been suggested for the complexes. Antibacterial and antifungal screening of the ligands and their complexes reveal that all the complexes show higher activities than the ligands. The antioxidant activities of the ligands and complexes were determined by superoxide and hydroxyl radical scavenging methods in vitro, indicating that the complexes exhibit more effective antioxidant activity than the ligands alone. The results show that the Cu(II) complexes also have similar superoxide dismutase activity to that of native Cu, Zn-SOD. All complexes exhibit suitable Cu(II)/Cu(I) redox potential (E_1/2) to act as synthetic antioxidant enzyme mimics.     

Copper(II) complexes of potentially terdentate N2-[(R)-2-hydroxypropyl]- and N2-[(S)-2-hydroxypropyl]-(S)-phenylalaninamide for chiral recognition: Synthesis of the Ligands and Formation Constants

Copper(II) complexes of the ligands N²-[(R)-2-hydroxypropyl]- and N²-[(S)-2-hydroxypropyl]-(S)-phenylalaninamide performed chiral separation of N-dansyl-protected and unmodified amino acids in HPLC (reversed phase). With the aim of investigating which species are potentially involved in the discrimination mechanism, the two ligands were synthesized and their complexation equilibria with Cu²⁺ studied by potentiometry and spectrophotometry in aqueous solution up to pH 11.7. The formation constants of the species observed, [CuL]²⁺, [CuL₂]²⁺, [CuLH_–1]⁺, [CuL₂H_–1]⁺, [CuL₂H_–2], and [CuL₂H_–3]^?, were quite similar for both compounds and were compared to those of (S)-phenylalaninamide. Most probably, in [CuL₂H_–3]^? the ligands behave as terdentate, with the deprotonated OH group occupying an apical position.     

Binary and ternary complexes of Cu(II) ions with saccharin and cysteine

The square-wave voltammetric behaviour of cysteine and saccharin was studied at a static mercury drop electrode at pH 7.4 in the presence of Cu(II) ions. In the presence of excess Cu(II), cysteine exhibited three reduction peaks for Hg(SR)₂ (−0.086 V), free Cu(II) (−0.190 V) and Cu(I)SR (−0.698 V), respectively. Saccharin produced a catalytic hydrogen peak at −1.762 V. In the presence of Cu(II), saccharin gave a new peak (−0.508 V), corresponding to the reduction of Cu(II)–saccharinate, which in the presence of cysteine formed a mixed ligand complex (−0.612 V), CuL₂A₂ (L=saccharin and A=cysteine). The peak potentials and currents of the obtained complexes were dependent on the ligand concentration and accumulation time. The stoichiometries and overall stability constants of these complexes were determined by Lingane's method (voltammetrically) and Job’s method (spectrophotometrically). The mixed ligand complex in the molar ratio 1:2:2 (log β=33.35) turned out to be very much stronger than the 1:1 Cu(I)SR (log β=21.64) and 1:2 Cu(II)–saccharinate (log β=16.68) complexes. Formation of a mixed ligand complex can be considered as a type of synergism.     

A Novel Approach to Monitoring of the Diffusion Junction Potential in Speciation Studies by Polarography under very Acidic Conditions. Part II: The Quasi‐Reversible Cu(II)‐Picolinic Acid System

The use of polarography to accurately determine stability constants of complexes formed under very acidic conditions (below pH 2) is demonstrated. The diffusion junction potentials, which must be accounted for below pH 2, were evaluated by applying protocols developed where Tl(I) is used as an internal reference. The Cu(II)‐picolinic acid (2‐pyridinecarboxylic acid) system studied was chosen since the CuL⁺ species only exists in solution below pH 2 under the conditions used and literature data exists to confirm the accuracy of procedure. Additionally, the reduction of Cu(II) was quasi‐reversible and procedures to determine the reversible half‐wave potentials were investigated. Average log β values of 7.75±0.09 for CuL⁺ and 14.8±0.1 for CuL₂ were obtained, which compared well to literature data.     

EPR studies of copper(II) complexes with poly-2-methyl-5-vinyl-pyridine and poly-2-vinylpyridine

Cu(II) complexes of poly-2-vinylpyridine (P2VP) and poly-2-methyl-5-vinylpyridine (P2M5VP), partially quaternized by dimethylsulphate, and of the analogues (2-methyl-5-ethylpyridine, 2-ethylpyridine) were studied by EPR spectroscopy in a mixture of methanol and water. Peculiarities of the complex formation reaction were observed for the polymers compared to the analogues. At ratios of [Py]:[Cu²⁺] > 40, the predominant formation of tetrapyridinate-Cu(II) species [(CuL₄)]²⁺ was found for P2M5VP. However, differences were found between the parameters of EPR-spectra for the [CuL₄]²⁺ in the polymer from that of the [Cu(2M5EPy)₄]²⁺. It was suggested that, in the polymer, [CuL₄]²⁺ complexes with structure intermediate between square planar and tetrahedral are formed. Moreover, the maximum value of the pyridine fraction forming [CuL₄]²⁺ in P2M5VP was found to be about 10% and it is appreciably less the value of the fraction in P4VP (about 40%). For P2VP at [Py]:[Cu²⁺] > 40, an insignificant amount of [CuL₁]²⁺ and [CuL₂]²⁺ are formed in the solution. It follows that the main chain position relative to the ligand nitrogen atom in these polyvinylpyridines affects profoundly the complexation between the macromolecules and Cu(II) ions. The steric hindrances due to the chain are likely to change the [CuL₄]²⁺ structure and to prevent complex formation for P2VP.     

Interaction of Co(II), Ni(II), Cu(II), and Zn(II) with 12- and 14-membered macrocycles containing O2N2 donors

The 12- and 14-membered diazadioxo macrocyclic ligands, 1,2?:?7,8-diphenyl-6,9-diaza-3,12-dioxocyclododecane (L¹) and 1,2?:?8,9-diphenyl-7,10-diaza-3,14-dioxocyclotetradecane (L²), were synthesized by condensation between o-phenylenediamine, 1,2-dibromoethane/1,3-dibromopropane, and catechol. Metal complexes [ML¹Cl₂] and [ML²Cl₂] [M?=?Co(II), Ni(II), Cu(II), and Zn(II)] were prepared by interaction of L¹ or L² with metal(II) chlorides. The ligands and their complexes were characterized by elemental analyses, IR, ¹H, and ¹³C NMR, EPR, UV-Vis spectroscopy, magnetic susceptibility, conductivity measurements, and Electrospray ionization-mass spectral (ESI-MS) studies. The results of elemental analyses, ESI-MS, Job's method, and conductivity measurements confirmed the stoichiometry of ligands and their complexes while absorption bands and resonance peaks in IR and NMR spectra confirmed the formation of ligand framework around the metal ions. Stereochemistry was inferred from the UV-Vis, EPR, and magnetic moment studies.     

A hexanuclear discrete assembly and a two dimensional coordination polymer constructed from heterotrinuclear [(CuL)2Zn]2+ nodes and dicyanamide spacer (H2L = salen type Schiff base ligands)

Two new Cu(II)–Zn(II) complexes as a discrete hexanuclear cluster [{(CuL¹)₂Zn}₂(μ_1,5-N(CN)₂)₂](ClO₄)₂ (1) and a two dimensional (2D) coordination polymer [(CuL²)₂Zn(μ_1,5-N(CN)₂)₂]_n (2) have been isolated by mixing two similar tetradentate Schiff bases H₂L¹ (N,N′-bis(ɑ-ethylsalicylidene)-1,3-propanediamine) and H₂L² (N,N′-bis(salicylidene)-1,3-pentanediamine) separately with Cu(ClO₄)₂·6H₂O, Zn(ClO₄)₂·6H₂O and NaN(CN)₂ ?at same reaction condition. The heterometallic complexes have been structurally characterized by single crystal X-ray analyses showing that both are formed by angular trinuclear nodes and μ_1,5-dicyanamide spacers. The trinuclear nodes ([(CuL¹)₂Zn]²⁺ in 1 and [(CuL²)₂Zn]²⁺ in 2 are produced in situ from their corresponding reactants. The two Schiff base ligands coordinating the Cu(II) ions through the N₂O₂ donor set are additionally bonded to a Zn(II) ion with the four phenoxido oxygen atoms that act as bridging atoms. The zinc ion completes its coordination geometry with two terminal nitrogen atoms of two different dicyanamide spacers. The orientation of spacers from zinc ion are convergent in 1 whereas divergent in 2. Thus, two [(CuL¹)₂Zn]²⁺ nodes are interconnected by double μ_1,5-dicyanamide bridges via Zn(II) centres to form discrete hexanuclear assembly of complex 1. On the other hand, [(CuL²)₂Zn]²⁺ nodes in 2 are joined by μ_l,5-dicyanamide that bridge Zn(II) to Cu(II) centres of symmetry related units in order to construct a 2D coordination polymer. Consequently, the final coordination environment around Zn(II) is octahedral in both complexes whereas that around Cu(II) are square planar and square pyramidal in 1 and 2 respectively.     

Influence of the proline residue on the co-ordination of Cu(II) to peptides containing -Pro- and -Pro-Pro- subunits

The synthesis of the series of peptides identified in the neuropeptide Nereidine, (Pro-Pro-Gly)_n where n = 1, 2 or 3, is reported together with a potentiometric and spectroscopic study of their complexes with Cu(II) at 25°C and I = 0.10 mol dm⁻³ (KNO₃). All three peptides behave similarly, forming [CuL] species at low pH followed by [CuL₂ and, at higher pH, [CuH₋₁L]. This complex involves co-ordination through the amide nitrogen of the first glycine residue forming an eight-membered chelate ring. Increase in the length of the peptide chain (i.e. increasing n from 1 to 2 or 3) does not affect the complexed species formed. The results of a potentiometric study of the Cu(II) complexes of the series of tetrapeptides Pro-Ala-Ala-Ala, Ala-Pro-Ala-Ala, Ala-Ala-Pro-Ala and Ala-Ala-Ala-Pro are also reported. The behave similarly to complexes of the analogous ligands based on glycine, showing an even clearer “break-point” effect in Cu(II) co-ordination.     

Cuprous complexes and dioxygen,VII. Competition between one- and two-electron reduction of O2 in the autoxidation of Cu(1-methyl-2-hydroxymethyl-imidazole)2+

The complexation of 1-methyl-2-hydroxymethyl-imidazole (L) with Cu(I) and Cu(II) has been studied in aqueous acetonitrile (AN). Cu(I) forms three complexes, Cu(AN)L⁺, CuL₂⁺, and Cu(AN)H_?1L, with stability constants logK(Cu(AN)⁺ + L ? Cu(AN)L⁺) = 4.60 ± 0.02, logβ₂ = 11.31 ± 0.04, and logK(Cu(AN)H_?1L+H⁺ ? Cu(AN)L⁺) = 10.43 ± 0.08 in 0.15M AN. The main species for Cu(II) are CuL²⁺, CuH_?1L⁺, CuH_?1L₂⁺, and CuH_?2L₂. The autoxidation of CuL₂⁺ was followed with an oxygen sensor and spectrophotometrically. Competition between the formation of superoxide in a one-electron reduction of O₂ and a path leading to H₂O₂ via binuclear (CuL₂)₂O was inferred from the rate law with k_a = (2.31 ± 0.12) · 10⁴M ^?2S ^?1, k_b = (1.0 ± 0.2) · 10³M ^?1, k_c = (2.85 ± 0.07) · 10²M ^?2S ^?1, k_d = 3.89 ± 0.14M ^?1S ^?1, k_e = 0.112 ± 0.004, k_f = (2.06 ± 0.24) · 10^?10M S ^?1, k_g = (1.35 ± 0.07) · 10^?7 S ^?1, and k_h = (6.8 ± 1.4) · 10^?7M ^?1 S ^?1.     

Ni(II) and Cu(II) complexes of new unsymmetrical N2O2 Schiff bases derived from 3-(2-aminobenzylimino)-1-phenylbutan-1-ol: synthesis,structure, antibacterial properties,and electrochemistry

Two new N₂O₂ unsymmetrical Schiff bases, H₂L¹ = 3-[({o-[(E)-(o-hydroxyphenyl)methylideneamino]phenyl}methyl)imino]-1-phenyl-1-buten-1-ol and H₂L² = 3-[({o-[(E)-(2-hydroxy-1-naphthyl)methylideneamino]phenyl}methyl)imino]-1-phenyl-1-buten-1-ol, and their copper(II) and nickel(II) complexes, [CuL¹] (1), [CuL²] (2), [NiL¹] (3), and [NiL²] (4), have been synthesized and characterized by elemental analyses and spectroscopic methods. The crystal structures of these complexes have been determined by X-ray diffraction. The coordination geometry around Cu(II) and Ni(II) centers is described as distorted square planar in all complexes with the CuN₂O₂ coordination more distorted than the Ni ones. The electrochemical studies of these complexes indicate a good correlation between the structural distortion and the redox potentials of the metal centers. The ligand and metal complexes were also screened for their in vitro antibacterial activity.     

Synthesis,complex formation kinetics and thermodynamic study of some acyclic polyamine and N2O2 ligands with copper(II)

The polydentate ligands, 3-(2-aminocyclohexylamino)-2-(2-aminocyclohexyl aminomethyl) propionic acid (L¹ ), 4,7,10-triazatridecanedinitrile trihydrochloride (L² ), and 2,2′-(ethane-1,2-diyl) bis(methylazanediyl) diethanol (L³ ) were prepared and their structures investigated by FT-IR, NMR, and MS. The kinetics of complex formation between Cu(II) and L¹, L², and L³ were investigated in acidic aqueous solutions using the stopped-flow method. The stability constants of the complexes were determined by spectrophotometric titration (T?=?293?K, μ?=?0.1?mol?L^?1 NaClO₄), using a diode array UV-Vis spectrophotometer equipped with peristaltic pump and pH meter. The stability constants for the complexes were CuL^1?>?CuL^2?>?CuL³. Activation enthalpies (ΔH#) of these complexes were 55?kJ?mol^?1 for CuL¹, 61?kJ?mol^?1 for CuL², and 36?kJ?mol^?1 for CuL³, respectively.