Spectrochemical Properties of Noncubical Transition Metal Complexes in Solutions. XIV. Angular Overlap Studies of bis(Salicylidene-2-aminothiazole)Copper(II) in Various Solvents

The copper(II) complex [Cu(sat)], where Hsat is salicylidene-2-aminothiazole (bidentate Schiff - base), was studied in variety of solvents. In the solid state, the complex is black. It has been characterized by elemental analysis, solubility in common solvents, molar conductivity, and ultraviolet (UV) and visible (Vis) spectroscopy. The complex is easily soluble in common solvents such as chloroform, dimethylformamide, dimethyl sulfoxide, and 1,4-dioxane. The known crystal structure of similar compounds shows planar coordination geometry for the copper center. Combined multitechnique experiments have been applied to confirm the structure of the complex in solutions. The molar conductivities indicate their nonelectrolyte properties in all these solvents. The spectroscopic measurements were used to study the coordination properties of donoratoms and their bonding abilities.     

9-羟基-芴-9-羧酸双核铜配合物[Cu(C_(14)H_8O_3)(C_9H_7N)(C_2H_5OH)]_2的合成、晶体结构及热稳定性研究

在自然界中,α-羟基羧酸广泛的存在于动植物体内,在羧酸循环、碳水化合物代谢和氨基酸的合成中起到重要的作用。Tapscott等详细总结了有关羟基羧酸及其金属配合物的合成化学[1]。芴的9位上2个氢原子被羟基和羧基取代可生成9-羟基-芴-9-羧酸(简称芴酸),它是α-羟基乙酸的衍生物,是一种具有生理活性的植物生长整形素,它能够延缓植株生长,影响植株根的向地性和茎的向光性[2]。由于芴酸含有羟基和羧基两种不同的氧配位原子,使其又可以作为一种潜在的构筑配合物的组织基元。目前有关芴酸与金属离子的合成与结构化学研究相对较少,仅见铜、镉的单…     

Manifestation of diamagnetic chemical shifts of proton NMR signals by an anisotropic shielding effect of nitrate anions

A remarkable upfield shift of the py_α protons of complexed 2,2′-bipyridine in [cis-Pd(bpy)(NO₃)₂] is observed which is considered to originate from the anisotropic influence of suitably positioned coordinated nitrate anions around the Pd(II) centre of the molecule. A typical complexation-induced downfield shift is observed for the NH₂ protons in [cis-Pd(en)(NO₃)₂] where ‘en’ stands for ethylenediamine.     

Synthese und Kristallstruktur von Blei(II)‐oxidhalogenid‐Alkoholaten mit unterschiedlichen Verknüpfungsvarianten von Pb4O4‐Heterokubaneinheiten

Synthesis and Crystal Structure Determination of Lead(II) Oxide Halide Alcoholates with Different Connectivity of Pb₄O₄ Heterocubane‐like Subunits The reaction of red lead(II) oxide (Litharge) and lead(II) halide (Cl^? and Br^?) with diethylene glycole at a temperature of 180 °C leads to the isotypic compounds [Pb₆(C₄H₈O₃)O₂Cl₆] (1) and [Pb₆(C₄H₈O₃)O₂Br₆] (2) . In a similar synthesis with PbI₂ as educt at temperature of 160 °C the two modifications β‐[Pb₆(C₄H₈O₃)O₂I₆] (3) and α‐[Pb₆(C₄H₈O₃)O₂I₆] (4) were found, whereas at a reaction temperature of 180 °C [Pb₉(C₂H₄O₂)(C₄H₈O₃)O₃I₈] (5) was surprisingly obtained as product. The X‐ray diffraction data show that at a temperature of 180 °C a splitting of the ether took place. The cited compounds show cubane like subunits built by lead and oxygen atoms. These fragments are connected by alkoholate molecules. In 5 additionally an I₆ octahedra centered by lead is observed.     

Complexing properties of methyl and phenyl glycine derivatives in their compounds with H+, Ni(II), Cu(II), and Zn(II)

The influence of the solvent and the substituents on the complexing properties of methyl and phenyl glycine derivatives is discussed. On the basis of a computer analysis of potentiometric titration results, the composition and the stability constants of the complexes ofN-methylglycine,N,N-dimethylglycine,N-phenylglycine and phenylglycine with H⁺ and with Ni(II), Cu(II), Zn(II) were determined. The ligand-metal coordination mode as well as the zwitterion level in percent in ligand/proton systems were determined by spectral analyses and equilibria studies.

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Komplexbildung der Methyl- und Phenylglycin-Derivate in ihren Verbindungen mit dem Proton und Ni(II), Cu(II) und Zn(II)

Zusammenfassung Der Einfluß des Lösungsmittels und der Substituenten auf die komplexbildenden Eigenschaften der Methyl- und Phenylglycin-Derivate wird diskutiert. Anhand einer Computer-Analyse von potentiometrischen Daten wurden die Zusammensetzung und die Beständigkeitskonstanten der Komplexe vonN-Methylglycin,N,N-Dimethylglycin,N-Phenylglycin und Phenylglycin mit H⁺, Ni(II), Cu(II) und Zn(II) festgestellt. Mittels spektroskopischer Methoden und Gleichgewichtstudien wurde der Koordinationstyp des Liganden mit dem Metall festgestellt sowie der Prozentanteil des Zwitterions im Ligand/Proton-System.

     

Synthesis, crystal structure and magnetic properties of a novel complex [Cu(NIT2Py)(PDA)(H2O)]·(CH3OH)(H2O)

A novel complex [Cu(NIT2Py)(PDA)(H₂O)]·(CH₃OH)(H₂O) has been synthesized and structurally characterized by X-ray diffraction methods. It crystallizes in the monoclinic space group P2(1)/c. The structure consists of [Cu(NIT2Py)(PDA)(H₂O)] moiety, one solvent methanol molecule and one water molecule. The copper(II) ion is in a distorted octahedral environment: one nitrogen atom and one oxygen atom from the NIT2Py, one nitrogen atom from the PDA (2,6-pyridine dicarboxylic acid) and one oxygen atom from the aqueous in the basal plane; two oxygen atoms from the PDA in the axial position. The units of [Cu(NIT2Py)(PDA)(H₂O)] were connected as one dimension chain by the intermolecular hydrogen bonds. The complex exhibits intramolecular antiferromagnetic interactions between the Cu(II) ion and the NIT2Py.     

Potentiometric studies on the complexation of copper(II) by phenolic acids as discrete ligand models of humic substances

Studies on the complexation of copper(II) by phenolic acids, as ligand models of humic substances were done by potentiometry. The acids under study were: 3,4-dihydroxyhydrocinnamic acid or hydrocaffeic acid (1), 3,4-dihydroxyphenylacetic acid (2) and 3,4-dihydroxybenzoic acid or protocatechuic acid (3). Acidity constants of the ligands and the formation constants of metal-ligand complexes were evaluated by computer programs. The carboxylic group of the phenolic acids has different pK_a1 values, being the dissociation constants intrinsically related with the distance between the function and the aromatic nucleus. The results obtained allow concluding that acidity constants of the catechol moiety of the compounds are similar with pK_a2 and pK_a3 values between 9.47-9.41 and 11.55-11.70. The complexation properties of the three ligands towards copper(II) ion are quite similar, being the species found not different either in nature or stability. Although the model ligands have some structural differences no significant differences were found in their complexation properties towards copper(II). So, it can be postulated that complexation process is intrinsically related with the presence of a catechol group.     

Synthesis and Crystal Structure of a New 2D Honeycomb-like Cadmium(II) Complex with Tripodal Ligand

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Thermal Behaviour and Decomposition Kinetics for Two Palladium(II) Complexes with 1-aminopyrene and its Derivative

The thermal decomposition studies for two palladium(II) complexes Pd(apyr)₂Cl₂ and Pd(pmpa)Cl₂ (apyr=1–aminopyrene and pmpa=N–(2–pyridylmethylene)–1–pyrenylamine) were carried out in pure nitrogen using TG-DTG techniques. The non-isothermal kinetic parameters for the two complexes were evaluated employing the method suggested by Málek, esták, Koga et al. Based on the above results, thermal behaviour of the complexes were carefully discussed, which showed that not only the parameters value, but also the decomposition pattern and mechanism for complex 1 are different from complex 2.This revised version was published online in November 2005 with corrections to the Cover Date.     

Dirhodium(II)-catalyzed carbonyl ylide generation. Stereoelectronic control in dioxolane formation

The combination of ethyl diazoacetate with aryl aldehydes in the presence of copper(I) or rhodium(II) catalysts results in the formation of 1,3-dioxolane products in moderate to good yields. These reactions occur through a pathway that involves ylide intermediates. Catalyst-dependent diastereocontrol is observed and suggests that metal-associated ylides are involved in the product-determining step. The influence of aryl aldehyde substituents has been determined. Current address. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 961–965, May, 1998.