Chelatbildende Enaminoketone I. Synthese von unsymmetrischen Liganden

Syntheses of chelating enaminoketones for a potential use in enrichment or recovery of metals from their aqueous solutions are described. Tridentate ligands were prepared either from aromatic amines, triethoxymethane and cyclic 1,3-dicarbonyl compounds in a one-step synthesis, or from the anilinomethylene compounds obtained by this approach and aliphatic amines. Polymerizable ligands have also been synthesized by reaction with (meth)acryloyl chloride and copolymerized with styrene to yield a chelating polymer.

     

Spektroskopische Untersuchungen an organischen Carbonylverbindungen, 10. Mitt.: Vergleichende Absorptions-, Fluoreszenz- und NMR-Messungen an ausgewählten β-Diketonen und ihren BF2- und Be-Komplexen

Summary Be complexes of selected styryl-substituted -diketones were prepared and their absorption, fluorescence, and NMR spectra were measured. The data of these compounds are presented and compared with those of the analogous free ligands and their BF₂-complexes.

     

Zur Chemie der Pyrrolpigmente, 62. Mitt.

Sixteen diastereomeric 2,3-dihydrobilatrienes-abc substituted in position 3 with various chiral ligands, seven chiral derivatives of a 2,3-dihydrobilatriene-abc-12-propionic acid and a chiral derivative of a 8,12-bilatriene-abc-dipropionic acid were prepared. The chiroptical properties (CD) of these compounds were used as a monitor for the conformational influence of the various ligands. Therefrom it could be deduced that steric effects play a minor role in determining the topology of the chromophore. On the contrary, dipole-dipole interactions of the various partial moments of bile pigments and of the attached ligands crucially influence the conformational situation of the chromophore. This fact may be significant for the stabilization of certain chromophore conformations in biliproteids.

Herrn Prof. Dr.K. Winsauer zum 60. Geburtstag gewidmet.     

Über das komplexchemische Verhalten einiger substituierter 2-Merkapto-p-Kresole. II

Zusammenfassung Ein Verfahren zur Herstellung diverser Merkapto-Liganden wird angegeben. Merkaptide, Chelate und Mischligandkomplexe wurden präparativ hergestellt und beschrieben. Zur Konstitutionsermittlung werden IR-, NMR-, UV-VIS-Spektren und Elementaranalysen der Liganden und Ligand-Metall-Verbindungen angegeben und kommentiert. Unterschiedliche Wechselwirkungen zwischen Ligand und Ion, die infolge verschiedener Substituenten an der 6-Stelle auftreten, werden in einer Reihe von Versuchen aufgezeigt.

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The complexometric behaviour of some 2-mercapto-p-cresols. II

Summary A method for the preparation of ligands is given. Mercaptides, chelates and mixed-ligand-complexes are prepared and described. IR, NMR, UV-VIS spectra and elementary analysis for the investigation of constitution of the ligands and ligand metal compounds are given and commented. Unlike interactions between ligand and ion, appearing because of different substituents at the 6-position, are shown by a series of experiments.

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Herrn Prof. Dr. Gustav Zigeuner zum 60. Geburtstag gewidmet.     

Übergangsmetallkomplexe mit Nitronylnitroxylradikalliganden

The stable free radicals, the isomers of 4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide with the 2-substituentR (R=para-,meta-,ortho-pyridyl), have been prepared and used as ligands in copper(II), palladium(II) and platinum(II) complexes. The magnetic moments and the EPR spectra of the complexes and the free radicals have been investigated. Most of the complexes show a considerable intramolecular interaction between the radicalic groups of the ligands. No intramolecular interaction was found, however, between the transition metal ions and the unpaired electrons of the ligands. But by analysis of the EPR spectra in the solid state there was found in some cases an intermolecular interaction between the metal ion [copper(II)] and the unpaired electrons of the ligands.

     

Kupfer(II)-Komplexe mit para- und diamagnetischen Semicarbazonliganden

A series of complexes formed between the copper(II) metal ion and the semicarbazone of the stable free radical 2-acetyl-2,5,5-trimethyl-4-phenyl-3-imidazoline-3-oxid-1-oxyl and the analogous hydroxylamine has been prepared. By analysis of the IR spectra of the complexes the coordination mode of the ligands was determined.

     

Optisch aktive,aromatische Spirane, 9. Mitt.: Überprüfung eines Näherungsansatzes für Chiralitätsfunktionen bei 5,5′,6′-trisubstituierten 2,2′-Spirobiindanen

In order to test the semiempirical value of chirality functions in their mathematically most simple form 23 new optically active 5,5-disubstituted 2,2-spirobiindanes1 of known chirality and enantiomeric purity were prepared. Thus a set of about hundred compounds is now available with altogether sixteen types of ligands (i.e. substituents including hydrogen); the experimental molar rotation of fifteen compounds is used to determine the value of a ligandspecific parameter occuring in the used chirality polynomial. According to theory this polynomial is an approximation for the total rotation of derivatives with ligands of three different types and it approximates an experimentally separable part of the rotation as far as compounds with four different ligands are concerned.The additional chirality component, occurring exclusively in the case of derivatives with four different types of ligands turns out to be relatively small but not vanishing. Accordingly, the molar rotation predicted by our method is very good for disubstituted spirobiindanes of type1 and rather good for others with three different types of ligands but is distinctly worse for those with four different ligands. The numerical trend, however, is clearly represented even in cases where our calculation in principle refers to a part of the phenomenon only and the predicted absolute configuration is in call cases in agreement with the experiment.An adequate criterion to judge the quality of our approximation is introduced.

8. Mitt.:H. Neudeck undK. Schlögl, Mh. Chem.110, 541 (1979).     

Synthesis of aminophosphines containing a chiral dinaphthoazepine entity and their use in asymmetric catalysis

Summary Three azaphospha ligands with a chiral dinaphthoazepine subunit were prepared and used in asymmetric carbon-carbon bond forming reactions. The nickel catalyzedGrignard cross coupling reaction of 1-phenylethyl magnesium chloride and vinyl bromide afforded the product in up to 47% ee. The palladium catalyzed allylic substitution of 1,3-substituted propenylacetates with dimethyl malonate and the coupling of allylacetate with methyl N-(diphenylmethylene)-glycinate resulted in asymmetric inductions of up to 97% ee and 51% ee, respectively.

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Synthese von Aminophosphinen mit einer chiralen Dinaphthoazepineinheit und ihre Anwendung in der asymmetrischen Katalyse

Zusammenfassung Drei Azaphospha-Liganden mit einer chiralen Dinaphthoazepineinheit wurden dargestellt und in asymmetrischen Kohlenstoff-Kohlenstoff-Verknüpfungsreaktionen eingesetzt. Bei der nickelkatalysiertenGrignard-Crosskupplung von 1-Phenylethylmagnesiumchlorid mit Vinylbromid erhielt man das Kupplungsprodukt mit bis zu 47% ee. Die palladiumkatalysierte allylische Substitution von 1,3-substituierten Propenylacetaten mit Dimethylmalonat und die Kupplung von Allylacetat mit Methyl-N-(diphenylmethylen)-glycinat zeigten asymmetrische Induktionen von bis zu 97% bzw. 51% ee.

     

NMR determination of chemically related metals in solution as a new method of inorganic analysis

Summary An NMR spectroscopic method for the determination of chemically related metals in solution is suggested. The metals are determined in complexes with specially selected polydentate ligands. Structural requirements to ligands, analytical properties and general limits of the application of the method are discussed.

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NMR-Bestimmung chemisch verwandter Metalle in Lösung als neue Methode der anorganischen Analyse

     

New multidentate potential ionophors of ether-amide type

The syntheses of acyclic compounds featuring ether-amide groups and different terminal substituents are presented. Three series of new multidentate potential ligands were obtained.

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Neue mehrzähnige potentielle Ionophore des Ether-Amid-Typs

Zusammenfassung Es wird die Synthese acyclischer Verbindungen mit Ether-Amid-Gruppen und verschiedenen endständigen Substituenten beschrieben. Es wurden drei Verbindungsreihen erhalten, die neue potentielle mehrzähnige Liganden repräsentieren.

     

On the chemistry of pyrrole pigments,XCI: Copper complexes of pyridinologous linear tri- and tetra-pyrroles as cyclopropanation catalysts

Summary In addition to two recently described pyridinologous linear tri- and tetrapyrroles a biisoquinologous system was prepared and its geometrical features derived by means of NMR measurements and force field calculations. The copper complexes of these three ligands were isolated and characterized, and then used as catalysts in the cyclopropanation of styrene. The results were found to be similar to those reported for a variety of catalysts in literature. Thus, it was demonstrated that these systems can be used in principle as catalysts.

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Zur Chemie von Pyrrolpigmenten, 91. Mitt.: Kupferkomplexe pyridinologer linearer Tri- und Tetrapyrrole als Katalysatoren für die Cyclopropanierung

Zusammenfassung Zusätzlich zu zwei jüngst beschriebenen linearen pyridinologen Tri- und Tetrapyrrolen wurde ein biisochinolylanaloges System dargestellt und seine Geometrie aus Kernresonanzmessungen und Kraftfeldrechnungen abgeleitet. Die Kupferkomplexe dieser drei Liganden wurden isoliert und charakterisiert und als Katalysatoren für die Cyclopropanierung von Styrol eingesetzt. Die Ergebnisse waren mit jenen aus der Literatur zahlreicher Komplexe vergleichbar. Damit konnte gezeigt werden, daß solche Systeme prinzipiell als Katalysatoren Verwendung finden können.

     

Complexes of some platinum group metals with hydrazone ligands and their catalytic oxidative properties

Summary New complexes of ruthenium(II), ruthenium(III), osmium(III) and palladium(II) have been prepared with a neutral bidendate hydrazone ligand derived from antipyrine-4-carboxaldehyde and benzoylhydrazine. Ruthenium(III) complexes have also been synthesized from monobasic bidendate ligands prepared from benzaldehyde and benzoyl orp-substituted (Me, Cl) benzoyl hydrazine. The complexes were characterized by spectroscopic techniques and investigated by cyclic voltammetry. The efficient catalytic oxidation of alcohols and 3,5-di- ^t butyl catechol in the presence of N-methylmorpholine-N-oxide orm-chloroperbenzoic acid as co-oxidants is reported.

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Komplexe einiger Platinmetalle mit Hydrazonliganden und ihre katalytischen oxidativen Eigenschaften

Zusammenfassung Neue Komplexe von Ru(II), Ru(III), Os(III) und Pd(II) mit einem aus Antipyrin-4-carbaldehyd und Benzoylhydrazin hergestellten neutralen bidentaten Hydrazonliganden wurden synthetisiert. Im Fall von Ru(III) wurden auch aus Benzaldehyd und verschiedenen Benzoylhydrazinen gewonnene monobasische bidentate Liganden eingesetzt. Die Komplexe wurden mittels spektroskopischer Methoden charakterisiert und mit Hilfe der cyclischen Voltammetrie untersucht. Es wird über die effiziente katalytische Oxidation von Alkoholen und 3,5-di- ^t Butyl-katechol in Gegenwart von N-Methyl-morpholin-N-oxid oderm-Chlorperbenzoesäure als Co-Oxidantien berichtet.

     

Neutral diamide ionophores — Phenylenedioxydiacetamides

The preparation of a series of neutral ligands containing ether and amide groups is described. These ligands as well as related ones bearing other diamide groups are shown to selectively chelate Group II A cations by picrate extraction from water to methylene dichloride. This result was also confirmed by atomic absorption measurement. The changes in UV absorption of aromatic rings and amide groups in the ligands upon titration with metal salts in methanol allow the estimation of the ordering of cation binding.

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Neutrale Diamid-Ionophore — Phenylendioxyacetamide

Zusammenfassung Die Darstellung einer Reihe von neutralen Liganden mit Ether- und Amidgruppen wird beschrieben. Sowohl diese Liganden — als auch verwandte mit anderen Diamidgruppen — bilden mit Kationen der Gruppe II A selektiv Chelate, wie durch Pikratextraktion aus wäßriger Lösung gezeigt wurde. Dieses Ergebnis wurde auch durch Messungen der Atomabsorption bestätigt. Die Änderungen in der UV-Absorption der aromatischen Ringe und der Amidgruppen in Methanol erlauben eine Abschätzung der Größenordnung der Kationenbindung.

     

Substituenteneinfluß auf die Bindung von Metallkationen an Amiden

The interactions of a series of cations with acetamide and its homologs is investigated using¹H-n.m.r. spectroscopy. The complexation of a cation by the amide induces changes in the electronic distribution of the ligands which lead to different chemical shifts in the n.m.r. spectra. The results are in agreement withab initio-calculations of the atomic population by the Mulliken Populations Analysis method using a minimal basis set.

     

Zur Chemie der Pyrrolpigmente, 56. Mitt.

From an investigation of the ICD of bilatrienes-abc and 2,3-dihydrobilatrienes-abc induced by mixtures of CCl₄ with (+)-cis-Pinane, (–)-lactic and (+)-tartaric acid esters it is concluded that specific interactions between chromophore and the chiral reagents afford a partial resolution of the labile racemate of helices. Attaching chiral residues covalently to the chromophore induces very low resolution of the same kind in case of apolar ligands like a cholesteryl-residue. However, with polar ligands as in the case ofBoc-lysyl derivatives enantiomeric excesses up to 90% are achieved depending on the solvent used.

Herrn Prof. Dr.Karl Schlögl zu seinem 60. Geburtstag gewidmet.     

Synthesis and spectroscopic studies of Sb(III) and Bi(III) complexes of semicarbazones

Summary New complexes of Sb(III) and Bi(III) with semicarbazones of the general formulae SbCl₃ L and BiCl₃ L (whereL=semicarbazones) have been prepared and characterized by IR,¹H- and¹³C-NMR spectral measurements. The results of the spectroscopic studies indicate that the semicarbazone ligands act as bidentate in all the complexes. All complexes are non-electrolytes inDMF solution. The molecular weight determinations indicate that the compounds are monomeric.

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Synthese und spektroskopische Untersuchungen von Sb(III)- und Bi(III)-Komplexen mit Semlcarbazonen

Zusammenfassung Es wurden neue Komplexe von Sb(III) und Bi(III) mit Semicarbazonen von der allgemeinen Formel SbCl₃ L und BiCl₃ L (L=verschiedenene Semicarbazone) dargestellt und mittels IR,¹H- und¹³C-NMR charakterisiert. Die spektroskopischen Untersuchungen zeigten, daß die Semicarbazon-Liganden in allen Komplexen zweizähnig agieren. Molekulargewichtsbestimmungen zeigten die monomere Natur der Verbindungen an.

     

Synthesis and structural studies of complexes of Sb(III) and Bi(III) with thiosemicarbazones

Summary Several new complexes of Sb(III) and Bi(III) with thiosemicarbazones of furfuraldehyde, thiophene-2-carbaldehyde, indol-3-carbaldehyde and pyridine-2-carbaldehyde have been prepared and characterized by elemental analysis, conductivity, molecular weight determination and IR,¹H-and¹³C-NMR spectral studies. The ligands form complexes of the typeMX ₃ L[M=Sb(III) or Bi(III);X=chloride;L=ligand] which are found to be non-electrolytes inDMF. Spectral data indicate that the thiosemicarbazones act as bidentate ligands through the azomethine nitrogen and sulphur.

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Synthese und Strukturuntersuchungen an Komplexen von Sb(III) and Bi(III) mit Thiosemicarbazonen

Zusammenfassung Es wurden einige neue Komplexe von Sb(III) und Bi(III) mit Tiosemicarbazonen von Furfural, Thiophen-2-carbaldehyd, Indol-3-carbaldehyd und Pyridin-2-carbaldehyd hergestellt und mittels Elementaranalyse, Leitfähigkeitsmessungen, Molekulargewichtsbestimmungen und IR-,¹H- bzw.¹³C-NMR-Spektroskopie charakterisiert. Die Komplexe sind vom TypMX ₃ L[M=Sb(III) oder Bi(III);X=Chlorid;L=Ligand] und sind inDMF Nichtelektrolyten. Die spektroskopischen Daten zeigen, daß die Thiosemicarbazone als zweizähnige Liganden über den Azomethin-Stickstoff und Schwefel wirken.

     

Oxovanadium(IV) complexes of halogenated oxines

Summary Six VO²⁺ complexes of 8-hydroxyquinoline (oxine) and of some of its mono- and dihalogenated derivatives have been prepared. The complex of 5-chloro-oxine is very unstable and oxidizes rapidly, generating a V(V) complex of stoichiometry VO(QCl)₂OH which could also be prepared in pure form. The infrared spectra of all complexes have been recorded and are discussed in detail. The complexes containing halogenated ligands appear as polymeric species, interacting through V=O...V=O bridges. The magnetic moments, investigated at room temperature, indicate completely quenched orbital contributions. The analysis of the electronic spectra reveals very complex solution behaviour including, oxidation phenomena, ligand loss, and interaction with the solvent.

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Oxovanadium(IV)-Komplexe von halogenierten Oxinen

Zusammenfassung Sechs VO²⁺-Komplexe von 8-Hydroxyquinolin (Oxin) und einige seiner mono- und dihalogenierten Derivate wurden dargestellt. Der Komplex des 5-Chloroxins erwies sich als besonders instabil und oxidiert sehr schnell unter Bildung eines V(V)-Komplexes der Stöchiometrie VO(QCl)₂OH, welcher auch in reiner Form dargestellt werden konnte. Die Infrarotspektren aller Komplexe wurden aufgenommen und werden eingehend diskutiert. Die Komplexe mit halogenierten Liganden erscheinen als polymere Spezies, welche über V=O...V=O-Brücken wechselwirken. Die bei Raumtemperatur gemessenen magnetischen Momente zeigen die totale Abwesenheit von Orbitalbeiträgen. Die Analyse der Elektronenspektren weist auf ein besonders kompliziertes Lösungsverhalten hin, welches Oxidationsphänomene, Ligandenabspaltung und Wechselwirkung mit den Lösungsmitteln einschließt.

     

Quantenchemische Untersuchungen zur Struktur und Bindung von Zr6 in Zirconium-Clusterverbindungen

EHT results for the metal core Zr₆ of zirconium cluster compounds are presented. In the case of CZr₆I₁₄ the influence of the interstitial atom and the ligands on the Zr–Zr distances and the chemical bond is discussed.

     

Neue Additionsverbindungen von Germaniumtetrajodid mit organischen Basen

Four new stable addition compounds have been prepared by reaction of germanium tetraiodide with various tertiary amines. It is a case of adducts of 1:4 composition, in contrast to the 1:5 addition compound with triethylamine, which we have also prepared and investigated for comparison. Formation, properties, analytical results, conductometric measurements and spectral data (IR and¹H-NMR) of these adducts are described and discussed in terms of possible structural types and the nature of the bonding.