Magnetic studied of a binuclear Cu(II) complex constructed from Cu(II) macrocyclic complex

A new binuclear copper(II) compound [(CuL)₂(Tpha)](ClO₄)₂ · 4H₂O (I), where L = 1,3,6,9,11,14-hexaazatricyclo[12.2.1.1^6,9]octadecane, Tpha = terephthalate dianion, has been constructed and structurally characterized by X-ray crystallography. Crystal analysis denotes that complex I crystallizes in the monoclinic system, space group P2₁/c with a = 11.115(2), b = 13.185(3), c = 16.184(3) Å and β = 105.68(3)°. Magnetic measurements confirm that I present an antiferromagnetic interaction between the paramagnetic ions.     

A trinucleating ligand based on 1,8-naphthalenediol: synthesis, structural and magnetic properties of a linear Cu(II)Cu(II)Cu(II) complex

The extension of Robson-type ligands from dinucleating based on 2,6-diformylphenol to trinucleating based on 2,7-diformyl-1,8-naphthalenediol is demonstrated by the synthesis, structural and magnetic characterization of the first trinuclear Cu(II) complex using a 1,8-naphthalenediol derived ligand.     

Reactivity and catalytic activity of a robust ruthenium(II)-triphos complex

The ruthenium(II)-triphos acetato complex [RuCl(OAc)(kappa3-triphos)] (triphos = (PPh2CH2)3CMe) has been found to be an active catalyst precursor for the hydrogenation of 1-alkenes under relatively mild conditions (5-50 bar H2, 50 degrees C). In contrast to related triphenylphosphine complexes, [RuCl(OAc)(kappa3-triphos)] is much less air sensitive and high catalytic activities were achieved when catalyst samples were prepared without exclusion of air or moisture. Substitution of the acetato ligand can be effected by treatment of acid, affording [Ru2(mu-Cl)3(kappa3-triphos)2]Cl and [RuCl(kappa3-triphos)]2(BF4)2 with aqueous HCl and [Et2OH]BF4, respectively, or by heating with dmpm in the presence of [NH4]PF6, resulting in formation of [RuCl(kappa2-dmpm)(kappa3-triphos)]PF6 (dmpm = PMe2CH2PMe2). A hydride complex, [RuHCl(kappa3-triphos)], formed by acetato-mediated heterolytic cleavage of dihydrogen is proposed as the active catalytic species. An inner-sphere, monohydride mechanism is suggested for the catalytic cycle, with chloro and triphos ligands playing a spectator role. These mechanistic proposals are consistent with reactivity studies carried out on [RuCl(OAc)(kappa3-triphos)] and [RuH(OAc)(kappa3-triphos)] and supported by a computational analysis. The solid-state structures of [RuCl(OAc)(kappa3-triphos)], [RuCl(kappa3-triphos)]2(BF4)2, and [RuCl(kappa2-dmpm)(kappa3-triphos)]PF6 have been established by X-ray diffraction.     

Proteolytic activity of Cu(II) complex of 1-oxa-4,7,10-triazacyclododecane

Proteolytic activity of the Cu(II) complex of 1-oxa-4,7,10-triazacyclododecane (oxacyclen) was compared with that of the Cu(II) complex of 1,4,7,10-tetraazacyclododecane by using albumin, gamma-globulin, and myoglobin as substrates. Values of kcat/Km were greater for Cu(II)oxacyclen by 40-80 times. The enhanced activity is attributed to the increased Lewis acidity of Cu(II) due to substitution of one nitrogen donor atom with oxygen.     

First example of a 2:1 cocrystal of mixed Cu(I)/Cu(II) complexes and a novel ferromagnetic bis(mu-hydroxo)dicopper(II) complex with a bis(pyrazol-1-yl)methane bidentate ligand

A unique 2:1 cocrystal of mixed Cu(I)/Cu(II) complexes [Cu(I)(H2CPz2)(MeCN)2](ClO4) (1) and [Cu(II)(H2CPz2)2(ClO4)2] (4), a novel ferromagnetic ClO(4-)-bridged bis(mu-hydroxo)dicopper(II) complex, [Cu2(H2CPz2)2(OH)2(ClO4)](ClO4)(CH3CN)(0.5) (5), and a bischelated copper(I) complex, [Cu(H2CPz2)2](ClO4) (2), prepared from a one-pot reaction of [Cu(MeCN)4](ClO4) and H2CPz2, are described. The structures of these complexes have been determined by X-ray crystallographic methods. The Cu(I)-N(acetonitrile) bond distances in complex 1 are nonequivalent (1.907(8) and 2.034(9) A), leading to the dissociation of one MeCN to form a Y-shaped complex, [Cu(I)(H2CPz2)(MeCN)](ClO4) (3), which is oxidized readily in air to form complex 5 with a butterfly Cu2O2 core.     

Thermal behaviour of Cu(II)-urea complex

The urea complex of copper was synthesized and its structure was established by Fourier transform infrared (FTIR), electron spin resonance (ESR) and atomic absorption spectroscopy and elemental analysis to be Cu(urea)₄Cl₂. The thermal behaviour of this complex has been studied by thermogravimetry and differential thermal analysis and FTIR and ESR. Thermal analysis shows that the decomposition of the complex occurs in four stages of weight loss of different intermediates followed by three endothermal effects. The complex is thermally stable up to 428 K. The ESR and FTIR behaviour of the Cu(II)-urea complex during thermolysis was studied between 428 and 633 K. The experimental results suggest that in this temperature range the complex decomposition occurred forming thermodynamically stable regions of Cu(II) which are ferromagnetically coupled.

---

Zusammenfassung Der Harnstoffkomplex von Kupfer wurde hergestellt, seine Zusammen-setzung ergab sich anhand von FTIR-, ESR- und Atomabsorptionsspektroskopie-Untersuchungen sowie Elementaranalyse mit der Formel Cu(Harnstoff)₄Cl₂.Mittels TG, DTA, FTIR und ESR wurde auch das thermische Verhalten dieser Komplexe untersucht. Die Thermoanalyse zeigte, daß der Zersetzungsprozeß über verschiedene Zwischen-produkte in vier Stufen mit Massenverlust verläuft, gefolgt von insgesamt drei endothermen Effekten. Bis 428 K ist der Komplex thermisch stabil. Das ESR- und FTIR-Verhalten des Cu(II)-harnstoffkomplexes bei der Thermolyse wurde im Temperaturbereich 428–633 K untersucht. Die experimentellen Ergebnisse lassen darauf schließen, daß bei der Zersetzung des Komplexes in diesem Temperaturbereich thermodynamisch stabile Regionen von ferromagnetisch gekoppeltem Cu(II) gebildet werden.

     

Cu(II)-triggered release of paclitaxel from a supramolecular complex

The research on the stimuli-responsive property of biological or synthetic macromolecules in a wide range of scientific fields is a crucial subject for the achievements of the targeted drug release and the precise control of the functions of the supramolecules at a molecular level. We used an anthraquinone-functioned cyclodextrin (1) bridged by an aza-arm to solubilise paclitaxel (PTX) by forming a supramolecular complex (1/PTX). The possible inclusion mode was given based on the experimental results of ultraviolet–visible spectroscopy, Fourier transform infrared, X-ray diffraction, fluorescence spectra, nuclear magnetic resonance, transmission electron microscope, scanning electron microscope and dynamic light scattering characterisations. The controlled release of PTX can be achieved by adding Cu²⁺ to the solution. This study provides useful references in developing stimuli-responsive drug-carrying and drug-releasing materials.     

1D coordination polymers of Cu(II) and Cu(II) dimers with a dicyanomethanide ligand

Several new 1D coordination polymers have been synthesised using the anionic ligand carbamoyldicyanomethanide, C(CN)₂(CONH₂)⁻ (cdm). The polymeric complexes [Cu(cdm)₂(py)₂]·2MeOH (1), [Cu(cdm)₂(4-Etpy)₂]·2MeOH (2), [Cu(cdm)₂(3,5-Me₂pzH)₂]·2MeOH (3) and [Cu(cdm)₂(3-HOCH₂py)₂]·2MeOH (4) (py = pyridine; 3,5-Me₂pzH = 3,5-dimethylpyrazole) contain Cu(II) atoms bridged by μ₂-(N,N′) cdm ligands between equatorial and axial coordination sites. The use of monodentate co-ligands brings about polymeric products, in contrast to the use previously of chelating co-ligands which facilitate the formation of discrete products. These 1D polymeric complexes are connected by hydrogen bonding between the amide functionalities and the lattice solvent. In the structures of 3 and 4 the neutral ligands also contain hydrogen bond donor groups that supplement the amide ring motif. Two other complexes have been obtained that are polymeric chains of alkoxide-bridged Cu(II) dimers. The complexes [Cu(cdm)(MeO)(2-amp)] (5) and [Cu(cdm)(dmap)] (6) (2-amp = 2-(aminomethyl)pyridine and dmap = dimethylaminopropoxide) are remarkably similar despite the different ligands that they contain. Bridging between dimers is via μ₂-(N,O) cdm ligands, consequently altering the nature of the hydrogen bonding between adjacent chains compared to the simple polymeric species 1–3.     

A liquid-state copper(II) ion-selective electrode containing a complex of Cu(II) with salicylaniline

A new liquid-state ion-selective electrode based on a complex of Cu(II) with salicylaniline is described. The electrode shows linear dependence of potential on the activity of Cu(2+) in the range from 5 x 10(-6) to 0.1M, with a slope of 28.3 mV/pCu at 18 degrees . The electrode shows a better selectivity relative to Ag(I) and Hg(II) than other copper(II) ion-selective electrodes. The possibilities for using the electrode for determination of copper in the presence of interfering cations are described.     

Reactivity of oxalates of La(III), Ba(II) and Cu(II) in ternary mixtures

Composites of cuprates of La(III) and Ba(II) were obtained by decomposing mixtures of oxalates of La(III), Ba(II) and Cu(II) prepared in 111 and 123 mol proportions respectively and sintering the oxide products at 1173 K. Reactions studied by TG, DTA and XRD techniques revealed the following features: (i) Decomposition of oxalates of La(III) and Ba(II) is drastically affected in mixtures. Decomposition temperature of organic part in the former (111) is shifted by 100 K while that of BaCO₃ in the case of latter (123) is shifted by 400 K towards lower temperature side. (ii) All exothermic peaks on DTA traces of both the mixtures are allotted to the decomposition of oxalates to Cu₂O, La₂O₂CO₃ and BaCO₃ phases while endothermic peaks around 863 and 1083 K are assigned for BaCuO₂ and La₂CuO₄ phases respectively in the case of former (111) and endothermic peaks at about 1068, 1136 and 1213 K are correlated with BaCuO₂, a composite of La₂O₃, La₂CuO₄ and La_0.5Ba_0.5CuO_3– (0.5) phases and LaBa₂Cu₃O_7– (0) phase respectively in the case of latter (123) and (iii) Lines of all cuprate compounds appear in XRD patterns of those samples preheated at temperatures 873 K. The following reaction is proposed in the case of 123 mixture: Authors are deeply thankful to the Authorities of Department of Atomic Energy (DAE), Goverment of India, for providing the funds for research project and to Professor A. V. Phadke, Department of Geology, University of Poona, for the valuable discussion.     

Reactivity of binary mixtures of Cu(II) oxalate and La(III) oxalate

Reactivity of binary mixtures of oxalates of Cu(II) and La(III) was studied by observing their thermal behaviours in decomposition using TG, DTA and XRD techniques to set the temperature conditions for preparations of various composites of oxides of Cu(II) and La(III). In the thermal behaviour it was found that the decomposition of Cu(II) oxalate is not affected while that of La(III) oxalate is drastically affected in the case of all the mixtures. The decomposition temperature at which La(III) oxide is formed is lowered by 250 K in the case of all the mixtures while the complete decomposition occurred at 723 K only in the case of mixtures containing excess Cu(II) oxalate.At 823 K La₂CuO₄ phase is developed in all the mixtures while -La and Cu₂La phases are also detected in mixtures containing excess Cu(II) oxalate. Therefore, the temperature 823 K was found to be suitable to prepare various composites viz. La₂CuO₄, La₂CuO₄·La₂O₃ and La₂CuO₄·CuO to study their electrical properties.Authors are thankful to the authorities of Department of Atomic Energy (DAE), Government of India, for providing the funds for research project and to Professor A. V. Phadke, Department of Geology, University of Poona, for valuable discussion.     

Metal exchange kinetics: uncatalyzed replacement of Ni(II) from tetramethylenediaminetetraacetatonickel(II) complex by Cu(II)

The kinetics of metal exchange between copper(II) and tetramethylenediaminetetraacetatonickel(II), [Ni(TMDTA)] has been studied between pH 3.4 and 4.8 at an ionic strength of 1.25 M (NaClO₄) and a temperature of 25.0 ± 0.1 °C. The reaction is first order in [Ni(TMDTA)]. The reaction order in [Cu²⁺] varies from first to zero and then back to first as [Cu²⁺] is increased. At low copper concentration, the first-order rate constant is pH independent and represents the attack of copper on the nickel complex through a pathway in which TMDTA is partially uncoordinated before reaction with copper. Evidence is presented for a stepwise dechelation mechanism followed by attack of copper to give a dinuclear intermediate. The zero-order rate is pH dependent. At higher [Cu²⁺], the swing back to first order is due to the formation of a weak copper-tetramethylenediaminetetraacetatonickelate complex which then converts to products through a dinuclear intermediate. A plausible mechanism, consistent with all the kinetic data, is presented.     

Reactivity of pyrrole pigments,XXI: Structure and reactivity of Cu(II) and Zn(II) bilindione chelates

Summary Several Mn, Cu, and Zn chelates of etiobiliverdin-IV-, mesobiliverdin-IX, and its dimethyl ester are studied. The results show that the chemical constitution of the Cu biliverdin chelate corresponds to a formal metal oxidation state of (II) coordinated to a neutral radical of the NH trideprotonated biliverdin. The reactivity of the Cu(II) bilindione chelates in nucleophilic solvents agrees with that expected for a neutral radical structure of the ligand; in CH₃OH, they undergo oxidation towards dimethoxybilipurpurins. The magnetic behaviour of Cu(II) etiobiliverdinate-IV- in the solid state shows an intramolecular weak antiferromagnetic coupling d⁹Cu-to--radical (J=–23 cm^–1) and an intermolecular weak antiferromagnetic coupling -radical-to--radical (J=–45 cm^–1). The analogy of this magnetic behaviour to that of the cation radical of metalloporphyrins is discussed.

---

Reaktivität von Pyrrolpigmenten, 21. Mitt.: Struktur und Reaktivität von Cu(II)- und Zn(II)-Chelaten von Bilindionen

Zusammenfassung Einige Mn, Cu and Zn Chelate von Etiobiliverdin-IV-, Mesobiliverdin-IX und seinem Dimethylester werden untersucht. Im Komplex koordiniert ein Metallatom (mit der Formalladung II) mit einem Neutralradikal des dreifach NH-deprotonierten Bilindions. Die Reaktivität des Komplexes gegenüber nukleophilen Lösungmitteln entspricht erwartungsgemäß dem eines neutralen -Radikals; in CH₃OH wird er zu Dimethoxybilipurpurin oxidiert. Bei Cu(II)-Etiobiliverdinat-IV beobachtet man im festen Zustand neben schwacher, antiferromagnetischer Kupplung zwischen d⁹Cu und -Radikal (J=–23 cm^–1) auch eine schwache, intermolekulare, antiferromagnetische Wechselwirkung zwischen zwei -Radikalen (J=–45 cm^–1). Dieses magnetische Verhalten wird dem des -Kationradikals von Metalloporphyrinen gegenübergestellt.

     

Tuning the coordination chemistry of a Cu(II) complex at high-pressure

Application of pressure on the Cu-complex CuAsp causes Jahn-Teller Cu-O bonds to be compressed, increasing the coordination environment from [4 + 1] to [4 + 2], highlighted by a discontinuity on compression of these bonding interactions.     

Homochiral 1D helical chain based on an achiral Cu(II) complex

Self-assembly of an achiral [Cu(L)] complex produced a homochiral helical chain [Cu(L)](3)·2H(2)O (1) (L = 2-dimethylaminoethyl(oxamato)). Interestingly, complex 1 obtained in our laboratory exhibits only a left-handed helical chain without any chiral source. Single-crystal X-ray analysis revealed the absolute structure and homochirality of its helical chain structure in the space group of P3(2). Solid-state circular dichroism (CD) spectra confirmed the high enantio excess of the crystals obtained in different synthesis batches. Magnetic susceptibility measurements reveal a relatively strong intrachain antiferromagnetic interaction between Cu(II) centers via an oxamato bridge (J = -74.4 cm(-1)).     

一个新型分子铁磁体: 氰根桥联的铜(II)-铁(III)配合物

合成和表征了一个新的分子磁体,氰根桥联的杂化型异金属配合物[Cu(en)]~3[Fe(CN)~6]~2.3H~O(en为乙二胺)。变温磁化率、零场冷却磁化强度(ZFCM)、场冷却磁化强度(FCM)和磁滞回线测量表明铜铁离子间存在着铁磁性相互作用,其铁磁相变温度为T~c=11.0K,矫顽力为20×10^-^4T,剩磁为1.70×10^-^1cm^3.mol^-^1.T。该化合物为杂化型铜(II)-铁(III)普鲁士蓝类中具有铁磁相变温度的首例。