Notiz über Parachloraldehyd

Ohne Zusammenfassung     

On Super-KMS functionals and entire cyclic cohomology

We formulate the super-KMS condition suggested by Connes and Kastler, in the context of entire cyclic cohomology of quantum algebras. We show that the Chern character of Jaffe, Lesniewski, and Osterwalder — associated by Kastler to a super-KMS functional — satisfies the entire growth condition. Hence, a super-KMS functional defines a cocycle for the entire cyclic cohomology of quantum algebras.Supported in part by the National Science Foundation.     

Reactions of lithiated 2,5-dimethylazaferrocene with selected electrophiles

Lithiation of 2,5-dimethylazaferrocene 1 with sec-BuLi/TMEDA in THF at −78 °C proceeds (as shown by quenching with D₂O) to comparable extent on the methyl groups and the Cp ring. However, the outcome of the reaction of the lithiated 1 with an electrophile depends on the nature of this electrophile. In the reaction with 4-methoxybenzaldehyde only the product originated from the lateral lithiation is formed, whereas the reaction with 4-methoxyacetophenone and 4,4′-dimethoxybenzophenone afforded mixtures of the products resulting from lateral and ring-lithiation. Similar results were also obtained in the reaction of lithiated 1 with chlorodiphenylphosphine and diphenyl diselenide. On the other hand, the exclusive formation of the Cp-substituted product was observed in the reaction of lithiated 1 with N,N-dimethylformamide. The structures of selected products (oily compounds were transformed into the corresponding crystalline W(CO)₅-complexes) were confirmed by X-ray diffraction. The presented reactions open a novel entry to specifically substituted azaferrocenes (especially those containing heteroatom substituents) with potential applications as ligands for the homogenous catalysis.     

Splitless injection of up to hundreds of microliters of liquid samples in capillary GC: Part II,experimental results

Sample evaporation in splitless injection of large volumes is rapid: depending on the experiment, results indicate that 200 μl of hexane, for instance, evaporates in 2–10 s, producing vapor at a rate of many hundreds of milliliters per minute. A 60 × 4 mm packed bed of 20–35 mesh Tenax TA enabled injection of 200 μl volumes of all solvents tested, and even 1 ml injections were possible provided they were performed over a period of 30 s. Retention of volatile sample components depends on the sample solvent, the injection volume, and the injection speed, but only little on the injector temperature. Losses of n-tridecane varied from hardly 15 % (when dissolved in pentane) to ca 60 % (ethyl acetate); losses of n-heptadecane were usually below 20 %. The column temperature during injection should be at least ca 20–30°C above the standard solvent boiling point.     

Metal‐Xenon Complexes

Long after the first isolation of a xenon compound in 1962 the first compounds with metal‐xenon bonds are prepared. The metal atoms are so far Au and Hg. The most stable metal xenon compounds decompose under loss of xenon slightly above room temperature. They can only exist if solvents and counter ions are weaker bases than atomic xenon. Solvents and counter ions used so far are HF, (SbF₆)^—, and (Sb₂F₁₁)^—.     

The platinum catalyst [bpyrPtCl2] in superacidic solution

The methane oxidation catalyst [bpyrPtCl(2)] (bpyr = bis-pyrimidine) dissolves in superacidic HF/SbF(5) solution under formation of a dinuclear cation [H(2)bpyrPt(mu-Cl)(2)PtbpyrH(2)](6+). Two crystal forms are isolated, [Pt(2)Cl(2)bpyr(2)H(4)](6+)(SbF(6)(-))(4)(Sb(2)F(11)(-))(2).2HF (I) (triclinic, Ponemacr;, a = 814.8(2) pm, b = 1444.8(3) pm, c = 2300.5(5) pm, alpha = 89.627(4) degrees, beta = 84.285(4) degrees, gamma = 84.665(4) degrees, Z = 2) and [Pt(2)Cl(2)bpyrH(4)](6+)(Sb(2)F(11)(-))(6).4HF (II) (triclinic, Ponemacr;, a = 879.4(2) pm, b = 1170.4(3) pm, c = 1789.9(5) pm, alpha = 95.37(2) degrees, beta = 99.97(2) degrees, gamma = 100.41(2) degrees, Z = 1). The cation in I has an angle of 148.4(1) degrees between the two square plane platinum environments, while the cation in II is fully planar. The non-platinum-bound nitrogen atoms are all protonated in the superacidic medium.