63Cu-NMR.-Untersuchungen von Kupfer (I)-Tetrapyridin-und Kupfer (I)-Tetraacetonitrilsolvaten

⁶³Cu-NMR.-Spectra of Cu(CH₃CN)₄X (X = ClO, BF, PF) and Cu(C₅H₅N)₄X (X = ClO, BF) in solution are reported at different temperatures and concentrations. The influence of temperature on the linewidth and chemical shift indicates an equilibrium of Cu(CH₃CN) and Cu(C₅H₅N) with another complex of lower symmetry. The preferential solvation of Cu (I) by pyridin in a mixture acetonitrile/pyridine is clearly shown.     

Eine Methode zur Bestimmung von Kupfer, Kupfer(I)-oxyd und Kupfer(II)-oxyd nebeneinander

Ohne Zusammenfassung     

Darstellung und Struktur von Tetraethylcyclotetraarsoxan-Komplexen von Kupfer(I)-Halogeniden

Preparation and Structure of Tetraethylcyclotetraarsoxane Complexes of Copper(I) Halides The polymeric complexes [Cu₄Cl₄{cyclo-(C₂H₅AsO)₄}₃]_n ( 1 ), [Cu₃Br₃{cyclo-(C₂H₅AsO)₄}₂]_n ( 2 ) and [Cu₆I₆{cyclo-(C₂H₅AsO)₄}₃]_n ( 3 ) were prepared by the reaction of (C₂H₅AsO)_n and CuX (X = Cl, Br, I) in acetonitrile and characterised by X-ray analysis. All three complexes contain only tetramers (C₂H₅AsO)₄ as ligands, in which the As₄O₄ ring systems coordinate between two and four Cu-atoms. In each case one As₄O₄ ring with a crown-shaped conformation is observed, which coordinates either four (in 1 ) or three (in 2 and 3 ) axially sited Cu-atoms. In addition there are further (C₂H₅AsO)₄ ligands, which display either a boat-chair- (in 1 ) or a twist-chair-conformation (in 1–3 ). The individual building units are connected to one another via Cu? X? Cu bridges (in 2 and 3 ) and/or centrosymmetric As₄O₄ ring systems (in 1–3 ) into chain ( 1 ) or layer structures ( 2 und 3 ).     

Darstellung und Fluoreszenzeigenschaften von Kupfer(I)-Carboxylaten

Preparation and Fluorescence Properties of Copper (I) Carboxylates By reduction of copper(II) carboxylates with ascorbic acid in aqueous solutions some aromatic copper(I) compounds can easily be obtained by precipitation. Powder x-ray photographs of copper(I) propionate and copper(I) monochloroacetate have similar characteristic interferences as copper(I) acetate, from which a layer structure is known. All the here described copper(I) carboxylates are fluorescent, indicating that oxygen atoms behave as sufficently strong donors, but most of them and especially those with tetragonal structure, do not change their fluorescence colour by cooling in liquid nitrogen like many copper(I) complexes with nitrogen bases do (fluorescence thermochromism). Fluorescence thermochromism occurs however at copper(I) 3-hydroxybenzoate. This presumably results from a lower symmetry.     

Die arsenometrische Bestimmung von Kupfer(I)- und Kupfer(II)-ionen nebeneinander

Ohne Zusammenfassung     

Komplexe von Kupfer(I) mit Glyoxal-bis-N-t.-butylimin

Formation of strongly colored complexes of Cu⁺ with glyoxal-bis-(N-t-butylimin) (GLI) is observed in acetonitrile. Optical measurements reveal two complexes, Cu(GLI)⁺ (?_max = 26.0 kK, δ = 2800) and Cu(GLI) (?_max = 19.3 kK, ε = 8530). The equilibrium constants (0.1M tetraethylammoniumperchlorate) are logK₁ = 3.9 and logK₂ = 2.5. The equilibrium data are confirmed by potentiometric measurements with a copper electrode. In O-donor solvents, only the 1:2 complex is observed. Cu(GLI)₂CIO₄ can be crystallized as a dark red solid which is stable towards atmospheric oxygen.     

Kathodische Chronopotentiometrie 1 von Kupfer(I) und Kupfer(II) in bromidhaltigen L?sungen

Ohne Zusammenfassung     

Darstellung und einige Eigenschaften von Kupfer(I)-Kupfer(II)-Selenocyanaten

Preparation and Some Characteristics of Copper(I)-Copper(II) Selenocyanates From the system Cu²⁺-H₂O-en-SeCN-in dependence on the conditions two new complexes have been prepared: Cu₃en₂(SeCN)(CN)₃· H₂O(I) and Cu₃en₂(SeCN)₂(CN)₂· H₂O(II). They were studied by the methods of infra-red and EPR spectra as well as by those of X-ray diffraction. It has been found that Cu₂₊ is coordinated in these complexes with two molecules of ethylene diamine and one molecule water. The anion ligands have a bridging function and coordinate the copper(I). The EPR spectra show that the two complexes exhibit around the atom Cu²⁺ have different ligand field symmetry. For complex (I) it is a typically axial spectrum with two values of the gfactor g⊥? 2.18 and g⊥? 2.05 while complex (II) has an asymmetrical isotropic spectrum with one g-factor value only g⊥? 2.07.     

Die photometrische Bestimmung von Kupfer als Kupfer (II)-aminoacetat

Ohne ZusammenfassungHerrn Prof. Dr. O. Glemser, Direktor des anorgan.-chemischen Instituts, danke ich für die Förderung der Arbeit durch Institutsmittel.     

Ascorbinometrische Bestimmung von Kupfer(II)-ionen

Zusammenfassung Es wurden mehrere Titrationsverfahren zur direkten reduktometrischen Bestimmung der Kupfer(II)-ionen mit Hilfe von Ascorbinsäuremaßlösung ausgearbeitet. Von den in verschiedenen Medien wie Mohrschem Salz + Kaliumrhodanid, Kaliumbromid + Natriumacetat, Natriumchlorid + Natriumacetat und schließlich Ammoniumchlorid + Natriumacetat durchführbaren Titrationen eignet sich die zuletzterwähnte am besten für praktische Analysenzwecke. Das Verfahren steht in bezug auf Genauigkeit und Reproduzierbarkeit der jodometrischen Bestimmung nicht nach, wird nur durch wenige Ionen gestört, und die zur Anwendung kommenden Reagentien sind alle sehr billig. Die ascorbinometrische Titration läßt sich visuell und unter Anwendung potentiometrischer Endpunktsanzeige im Makro- oder Mikromaße gut durchführen.Für die Ausführung einiger Versuche sagen wir Frau I. Buzás und Herrn Gy. Liptay verbindlichen Dank.     

Kupfer(I)-jodid-Reagenspapier und Fluorescenz-Thermochromie

The usual methods that are presently used for evaluation of potentiometric titrations make only partial use of the intrinsic information. Here is described a new method that processes all the data points that are generated in order to calculate concentration of the sample, pK-values and normal potential. Using the example of the titration of a single protonic acid we demonstrate that exact and reproducible results can be obtained in the range of pK-values from 4 to 11. In addition the time of measurement can be reduced by up to 80% without any loss in precision.     

Kupfer(I)-jodid-Reagenspapier und Fluorescenz-Thermochromie

Zusammenfassung Zahlreiche aromatische und aliphatische Stickstoffbasen bilden mit Kupfer(I)-jodid fluorescierende Verbindungen, die bei Abkühlung in flüssigem Stickstoff ihre Fluorescenzfärbung ändern. Zur analytischen Auswertung dieses Phänomens wurde ein Reagenspapier entwickelt.Verff. sind der Deutschen Forschungsgemeinschaft, dem Fonds der chem. Industrie und der Wiss. Gesellschaft Saar e.V. für die Förderung dieser Untersuchungen zu Dank verpflichtet.     

Über fluoreszierende Verbindungen von Kupfer(I)-jodid mit aromatischen Stickstoffbasen

On Fluorescent Compounds of Copper(I) Iodide with Aromatic Nitrogenous Bases The easily obtainable compounds of copper(I) iodide with esters of nicotinic acid, with nicotinic acid amide and nitrile, as well as with quinoline, isoquinoline and quinaldine are strongly fluorescent in ultraviolet light. They are remarkably stable against water and air, compared with analogous picoline and lutidine compounds. Only in one case (nicotinic acid hexyl ester-copper(I) iodide) the phenomenon of fluorescence thermochromism has been observed.     

Neue Kupfer(I,II)-Verbindungen

New Copper(I, II) Compounds Complexes of the type [Cu^II(N∩N)₂][Cu^ICl_1+x]_2x (N∩N = en, pn, 2-amino picoline) are prepared from Cu(N∩N)₂Cl₂ and copper(I) chloride. [Cu^II(enac)][Cu^ICl₂]₂ — a complex with a macrocyclic cation — is obtained, by the reaction of Cuen₂Cl₂ in aqueous acetone. Diacetyl monoxime partially reduces copper(II) of Cu(NSMe)₂Cl₂ and in this way causes the formation of [Cu(NSMe)_2][CuCl₃] (NSMe = β-aminoethyl methylsulfide). On the other hand a template reaction of this oxime with Cu(NSMe)₂ (ClO₄)₂ produces Cu^II(ONNSMe)(ClO₄) (HONNSMe?CH₃C(NOH)C(NCH₂CH₂SCH₃)CH₃), which shows a reduced paramagnetism. Basing on magnetic behaviour, i. r. and vis spectra the structure of the new compounds is discussed.     

Fluoreszenz-thermochrome Verbindungen von Kupfer(I)-jodid mit Äthyl- und Aminopyridinen

Fluorescent-Thermochromic Compounds of Copper(I) Iodide with Ethyl and Aminopyridines As formerly observed with analogous picoline and lutidine compounds, ethylpyridino and aminopyridino copper(I) iodide compounds are also fluorescent, and some of them show different fluorescence colours at room temperature and very low temperature (“fluorescence thermochromism”).     

Darstellung und Eigenschaften von Kupfer(II)-Hypophosphit

Thermal Behaviour of the Mixtures Na₂S? P₄S₁₀ and Na₄Ge₄S₁₀? P₄S₁₀ of the System Na₂S? GeS₂? P₄S₁₀ The mixtures of Na₂S? P₄S₁₀ and Na₄Ge₄S₁₀? P₄S₁₀ were investigated by DTA and DSC. In the system Na₂S? P₄S₁₀ the congruently melting compounds Na₃PS₄ and (NaPS₃)_x and the peritectic phase Na₄P₂S₇ were found. The IR-spectra are given. Glassy, anhydrous and hydrated Na₄Ge₄S_l0 were prepared and thermochemically characterized. The section Na₄Ge₄S₁₀? P₄S₁₀ is not quasibinary, the mixed cage-anion Ge_4?xP_xS₁₀^(4?x)? thus cannot be prepared by heating and annealing mixtures of Na₄Ge₄S₁₀ and P₄S₁₀.