Elektronenreiche Nickelkomplexe mit Heteroolefinen als Liganden

Nickel-Heteroolefin Complexes with High Electron Number The syntheses of complexes with nickel in the oxidation state zero and 15 different monodentate and bidentate heteroolefins (aldehydes, azomethines, 1,2-diimines, 1,2-diketons, α,β-unsaturated aldehydes, ketons and azomethines) are described. The composition of the complexes and the bond between the heteroolefins and the centralatom depend on the number and the kind of the heteroatoms in the ligands. In the 1,2-diimine complexes the nitrogen atom interacts with the nickel; an edge-on structure of the heteroolefins can be suggested for the complexes with aldehyds. I.r., H-n.m.r. and u.v./vis spectra and reactions are discussed.     

Methylcobaltverbindungen mit nicht chelatisierenden Liganden,IV. Monoolefinkomplexe

Methylcobalt Compounds with Non-chelating Ligands, IV. Monoolefin Complexes Tris(trimethylphosphane)cobalt(I) halides in ether solvents saturated with olefin at low temperatures from monoolefin complexes which are prone to dissociation. Upon reaction with methyl-or phenyllithium more stable compounds are formed of the composition CoR(CC)L₃ ( 1 – 4 ) (R  CH₃; CC  C₂H₄, C₃H₆, cyclo-C₅H₈; R  C₆H₅; CC  C₂H₄; L  P(CH₃)₃). In solution the fluctional molecules adopt a ground state structure containing a σ-bonded group and an olefin ligand in adjacent positions (trigonal-bipyramidal: CH₃ axial and C₂H₄ equatorial or C₆H₅ and C₂H₄ equatorial). The latter arrangement is confirmed for the crystalline state by an X-ray structure determination of (ethene)phenyltris(trimethylphosphane)cobalt ( 4 ). An equatorial plane of coordination along a Co P bond not only contains both ethene-C atoms but also all the atoms of the phenyl group. The compound is thermally decomposed to give biphenyl and (ethene)tris-(trimethylphosphane)cobalt(0). No products of an olefin insertion reaction are observed.     

Edelgasverbindungen mit dem Liganden –OTeF5

Noble Gas Compounds Containing the Ligand —OTeF₅ Xe(OTeF₅)₄, Xe(OTeF₅)₆, O?Xe(OTeF₅)₄ as well as mixed substituted derivatives O?XeF_x(OTeF₅)_4?x are described and discussed in context with the known compounds Xe(OTeF₅)₂, and Xe(OSeF₅)₂. The ligand —OTeF₅ is the best stabilizer for noble gas compounds, exceeded only by fluorine itself. Whereas the structures of Xe(OTeF₅)₄ and O?Xe(OTeF₅)₄ are analogous to XeF₄ and XeOF₄, Xe(OTeF₅)₆ is found to be structurally comparable to monomeric (gaseous) XeF₆. Attempts to isolate krypton compounds of the same type were not successful.     

Komplexierung von Be(II) mit gemischten Liganden

The complexation of Be(II) with mixed ligands viz. 3,5-dinitrosalicylic acid (3,5-DNS) and -resorcylic acid (-RSA) in aqueous 0.1M-KNO₃ medium has been investigated potentiometrically, which evince the formation of 111 complex.

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Polarographische Untersuchungen des Redoxverhaltens von Kupfer-Komplexen mit Liganden vom Cuprointyp

Polarographic Examination of the Redox Behaviour of Copper Complexes with Cuproin Type Ligands. Some copper(II)-complexes with ligands of the cuproin type 2,2′-dichinolyle (dichi), 3,3-dimethylene-4,4′-dimethyle-2,2′-dichinolyle (dmch) and 2,9-dimethyle-1,10-phenanthroline (dmp) were examined polarographically to their redox behaviour in methanol and acetonitrile. Concerning this strictly reversible redox system Cu(dmch) ? Cu(dmch)²⁺ + e^? in acetonitrile at 20°C the value E_1/2 = 0,605 ± 0,0025 V was evaluated.     

Isomere Kupfer(II)-Chelate mit Liganden vom Cuprointyp

Two pairs of isomeric copper(II) chelates of the composition Cu(dm)(NO₃)₂ and Cu(dp)(NO₃)₂, resp., have been prepared (dm=6,7-dihydro-5,8-dimethyl-dibenzo[b,j][1,10]phenanthroline), anddp=6,7-dihydro-5,8-diphenyl-dibenzo[b,j][1, 10]-phenanthroline). By ESR, IR, and visible reflectance spectra the structures of the first coordination sphere of these chelates have been established, the two Cu(dm) (NO₃)₂ chelates and the brown -Cu(dp) (NO₃)₂, having coordination number six while the green -Cu(dp) (NO₃)₂ has coordination number seven. In comparison with the diamagnetically diluted complexes (solution, powder) the isomerism is found to be typical only for undiluted copper(II) complexes.

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19. Mitt.:D. Rehorek, H. Spindler undPh. Thomas, Z. Chem.15, 281 (1975).