Fundamental Aspects of Ionic Dissociations: The Fragmentation Pathways of Excited Bicyclobutane Cations

A most recently developed method to quantify the fragmentation pathways of excited radical cations is presented. Using bicyclobutane cation as an illustrative example, the RRKM analysis of the breakdown diagram determined by He-Iα photoelectron-photoion coincidence spectroscopy is outlined. The results imply complete isomerization to 1,3-butadiene cation preceding the dissociative processes. The rate-energy functions of four competitive primary fragmentation reactions, leading to C₃H, C₄H, C₄H and C₂H are established. There is compelling evidence that the production of C₂H fragment ions does not compete effectively with these four reactions. The extent of kinetic and competitive shift effects is determined. The derived enthalpies of formation are in excellent accord with the available high quality reference data. The relative importance of different fragmentation pathways which ultimately lead to fragment ions of identical mass to charge ratio is assessed.     

Stability and accuracy of time discretizations for initial value problems

Summary This paper continues earlier work by the same authors concerning the shape and size of the stability regions of general linear discretization methods for initial value problems. Here the treatment is extended to cover also implicit schemes, and by placing the accuracy of the schemes into a more central position in the discussion general method-free statements are again obtained. More specialized results are additionally given for linear multistep methods and for the Taylor series method.This research has been supported by Swiss National Foundation, Grant No. 82-524.077This research has been supported by the Heinrich-Hertz-Stiftung, B 32 No. 203/79     

Growth and characterization of Mn- and Co-doped ZnO nanowires

A flow injection chemiluminescence method is proposed for the determination of cobalt, based on the strong catalytic effect of Cobalt(II) (1,10-phenanthroline)₃ complex on the lucigenin-periodate reaction in alkaline medium. Under the optimum experimental conditions, the chemiluminescence signal responded linearly to the concentration of cobalt(II) in the 1.0 × 10⁻⁹–3.0 × 10⁻⁷ g mL⁻¹ range with a detection limit of 4.4 × 10⁻¹⁰ g mL⁻¹ cobalt(II). The relative standard deviation for the determination of 5.0 × 10⁻⁸ g mL⁻¹ of cobalt was 2.3% in eleven replicated measurements. The method was successfully applied to the determination of cobalt(II) in pharmaceutical preparations.     

Photochemistry of 3-Substituted 1-Iminopyridinium Ylides. Regiospecific versus non-regiospecific photoisomerization patterns [1]

3-Substituted 1-iminopyridinium ylides 1 undergo photo-induced ring enlargement to 1H-1,2-diazepines. With strongly electron-withdrawing substituents the ring expansion process is regiospecific and leads exclusively to 4-substituted 1 H-1, 2-diazepines. Weak electron-donating substituents, like a methyl group and halogen atoms, do not have any directing effect since both 4- and 6-substituted 1 H -1,2-diazepines are obtained. With strong electron-donating substituents no diazepines are formed; instead one observes photo-induced isomerization to the 2-aminopyridine derivatives, the process being non-regiospecific. Regiospecific photo-induced ring expansion processes are explained in terms of a simple HMO model.     

Aristoserratin,ein neues Indolalkaloid aus Aristotelia serrata W.R.B. OLIVER und A. peduncularis (LABILL.) HOOK. F. 178. Mitteilung über organische Naturstoffe

Aristoserratine, a New Indole Alkaloid from Aristotelia serrata W.R.B. OLIVER and from A. peduncularis (LABILL .) HOOK . F. The new indole alkaloid aristoserratine (2) has been isolated from Aristotelia. Its structure and absolute configuration were elucidated on the basis of spectroscopic data.     

The Structure of the Alkaloid Peduncularine. Communication no. 172 on organic natural products

The revised structure 1 is put forward for peduncularine, the main alkaloid of Aristotelia peduncularis (Labill.) HOOK. F. (Elaeocarpaceae), on the basis of its spectroscopic properties and those of its degradation products, the Hofmann base 3 and the hydrogenation product 4 . Structure 1 represents the relative configuration of the alkaloid. Peduncularine belongs to the class of indole alkaloids with a monoterpene unit as the aliphatic portion. To our knowledge it constitutes the first example in which an isopropyl group has become detached from the terpene unit and occurs as a substituent on nitrogen.     

Sensitized photo-oxidation of methylcyclohexane as a thin film on seawater by irradiation with natural sunlight

Methylcyclohexane dissolved in and forming a thin film on purified seawater with traces of anthraquinone added as triplet sensitizer was exposed to natural sunlight in a quartz flask. The water was circulated through a glass cartridge filled with Amberlite XAD-2 for the concentration of reaction products which were identified by GC/MS after elution and silica gel chromatography. They included isomeric methylcyclohexanols as the principal components, primary hydroperoxides, a tentatively identified secondary peroxide, methylcyclohexanones, and acyclic ketones. Mass spectra and mechanisms are discussed as well as possible biological consequences of the formation of these compounds.     

Adsorption enrichment of some azo dye complexes on a carbon paste electrode and its application to the determination of small concentrations of cobalt and manganese

Summary The azo dyes eriochrome black T, eriochrome blueblack R and eriochrome blueblack B and their complexes with cobalt, manganese and magnesium show adsorption enrichment on carbon paste electrodes, dependent on the composition of the electrode filling. This effect may be used for the determination of cobalt and manganese by a.c. voltammetry in the 10^–7 to 10^–6 M range. Standard deviation has been found to be ± 3.2 and ± 3.5%, respectively.

---

Adsorptive Anreicherung einiger Komplexe von Azofarbstoffen an einer Kohlepasteelektrode. Anwendung zur Bestimmung geringer Konzentrationen von Kobalt und Mangan

Zusammenfassung Die Azofarbstoffe Eriochromschwarz T, Eriochromblauschwarz B und Eriochromblauschwarz R sowie ihre Komplexe mit Kobalt, Mangan und Magnesium werden adsorptiv an Kohlepasteelektroden angereichert. Die Anreicherung ist von der Zusammensetzung der Elektrodenfüllung abhängig. Anwendungen zur wechselstromvoltammetrischen Bestimmung von Kobalt und Mangan im 10^–7 bis 10^–6 M Bereich werden beschrieben. Die Standardabweichung liegt bei ± 3,2 bzw. ± 3,5%.

Die Untersuchungen wurden in dankenswerter Weise durch Mittel der Deutschen Forschungsgemeinschaft und des Verbandes der chemischen Industrie unterstützt.     

Self-assembly of tetrahedral and trigonal antiprismatic clusters [Fe4(L4)4] and [Fe6(L5)6] on the basis of trigonal tris-bidentate chelators

In a one-pot reaction, the tetranuclear iron chelate complex [Fe4(L4)4] 6 was generated from benzene-1,3,5-tricarboxylic acid trichloride (4), bis-tert-butyl malonate (5a), methyllithium, and iron(II) dichloride under aerobic conditions. Alternatively, hexanuclear iron chelate complex [Fe(L5)6] 7 was formed starting from bis-para-tolyl malonate (5b) by employing identical reaction conditions to those applied for the synthesis of 6. The clusters 6 and 7 are present as racemic mixtures of homoconfigurational (delta,delta,delta,delta)/(lambda,lambda,lambda,lambda)-fac or (delta,delta,delta,delta,delta,delta)/(lambda,lambda,lambda,lambda,lambda,lambda)-fac stereoisomers. The structures of 6 and 7 were unequivocally resolved by single-crystal X-ray analyses. The all-iron(III) character of 6 and 7 was determined by M?ssbauer spectroscopy.