Synthesis and Reactivity of the First Isolated Hydrogen‐Bridged Silanol–Silanolate Anions

We report on the first examples of isolated silanol–silanolate anions, obtained by utilizing weakly coordinating phosphazenium counterions. The silanolate anions were synthesized from the recently published phosphazenium hydroxide hydrate salt with siloxanes. The silanol–silanolate anions are postulated intermediates in the hydroxide‐mediated polymerization of aryl and alkyl siloxanes. The silanolate anions are strong nucleophiles because of the weakly coordinating character of the phosphazenium cation, which is perceptible in their activity in polysiloxane depolymerization.     

Experimental setup for the determination of analytes contained in ultrasonically levitated drops

An automated technique for the determination of analytes in an ultrasonically levitated sample of 2 to 5 microL volume has been developed. Contactless dosing of reagents or solvents into an ultrasonically levitated drop was realized via piezoelectric micropumps. Drop size was continually controlled with a programmed CCD camera. A diode array spectrometer designed for the use with optical fibers was used for absorption and fluorescence measurements. Determinations via direct absorption measurements following the method of standard addition and acid-base titrations with an absorption indicator and a fluorescent indicator were carried out. The mean consumption of sodium hydroxide added via a piezoelectric micropump in five successive titrations with 18 nmol of sulfuric acid inside a levitated drop (indicator bromothymol blue) had a relative standard deviation of 0.7% and differed only by 0.2% from the expected value.     

Synthesis and immobilization of quaternary ammonium cations in acidic zeolites

A general method for the synthesis of quaternary ammonium cations in acidic zeolites by a direct reaction of tertiary amines and alcohols is described.     

Spektroskopische Bestimmung der Doppelbindungslage in Phospholinen

Zusammenfassung Die Spin-Spin-Kopplungskonstanten der olefinischen Protonen mit dem ³¹P sowie die Feinstruktur der ¹H-NMR-Spektren sind charakteristisch für die Lage der Doppelbindung. Vielfach kann auch die Intensität der _C=C-Schwingung im IR zur Bestimmung der Doppelbindungslage benutzt werden. Massenspektren geben nur in Ausnahmefällen Hinweise, können jedoch zur exakten Bestimmung des Molekulargewichts dienen.

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Summary The spin-spin coupling constants of the olefinic protons with the phosphorus-31 as well as the fine structure of the nmr-spectra are characteristic for the position of the double bond. In the infrared, the intensity of the _C=C-frequency may often serve as indication of the position of the double bond. The applicability of mass spectra is limited to a small number of compounds. They may be used, however, for an accurate determination of the molecular weight.

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Die Ausführung der Untersuchungen erfolgte unter Mitarbeit von Herrn F. Dlugosch, Herrn H. Au und Fräulein R. Barth.

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Herrn Dr. C. A. Reilly, Shell-Development Company, Emeryville, USA, danken wir für die Überlassung getesteter Programmkartensätze zur Berechnung der NMR-Spektren.     

Stereoisomeric effects on mass spectra—I. A Review

The unimolecular reactions that give rise to mass spectra are controlled by spatial relationships and energy considerations. In molecules that contain a heteroatom, elimination reactions, involving bond-making as well as breaking, are often prominent, e.g. loss of water from alcohols. The ease of such reactions depends on spatial relationships in the molecule, and the resultant ion intensities in the spectra of geometric isomers can consequently be correlated with differences in geometry and hence furnish a basis for assigning structures. Processes that do not involve bond-making do not have such rigorous geometric requirements, but depend rather on attainment of a transition state defined in terms of a minimum energy content. Common product ions from stereoisomeric hydrocarbons seem often to arise via a common transition state. When this condition holds, the difference between the enthalpies of the isomers is reflected in the relative appearance potentials and–though the cause-and-effect relationship here is less direct and more readily obscured by other factors–relative intensities of the common product derived from the isomers. In both classes of processes, the spectra of stereoisomers can be simplified and made more distinctive by lowering source temperature and ionizing voltage.     

Pulsed-field gradient nuclear magnetic resonance study of transport properties of fluid catalytic cracking catalysts

Pulsed-field gradient nuclear magnetic resonance (PFG NMR) has been applied to study molecular diffusion in industrial fluid catalytic cracking (FCC) catalysts and in USY zeolite for a broad range of molecular displacements and temperatures. The results of this study have been used to elucidate the relevance of molecular transport on various displacements for the rate of molecular exchange between catalyst particles and their surroundings. It turned out that this rate, which may determine the overall rate and selectivity of FCC process, is primarily related to the diffusion mode associated with displacements larger than the size of zeolite crystals located in the particles but smaller than the size of the particles. This conclusion has been confirmed by comparative studies of the catalytic performance of different FCC catalysts.     

Combined raman elastic-backscatter LIDAR for vertical profiling of moisture,aerosol extinction,backscatter, and LIDAR ratio

A combined Raman elastic-backscatter lidar has been developed. A XeCl excimer laser is used as the radiation source. Inelastic Raman backscatter signals are spectrally separated from the elastic signal with a filter or grating polychromator. Raman channels can be chosen to register signals from CO₂, O₂, N₂, and H₂O. Algorithms for the calculation of the water-vapor mixing ratio from the Raman signals and the particle extinction and backscatter coefficients from both elastic and inelastic backscatter signals are given. Nighttime measurements of the vertical humidity distribution up to the tropopause and of particle extinction, backscatter, and lidar ratio profiles in the boundary layer, in high-altitude water and ice clouds, and in the stratospheric aerosol layer are presented. Daytime boundary-layer measurements of moisture and particle extinction are made possible by the improved daylight suppression of the grating polychromator. Test measurements of the CO₂ mixing ratio indicate the problems for the Raman lidar technique in monitoring other trace gases than water vapor.     

Raman-shifted laser sources suitable for differential–absorption lidar measurements of ozone in the troposphere

Received: 21 January 1997/Revised version: 20 May 1997     

Investigation of the reaction Dy164 (n, γ) Dy165

The level structure of Dy¹⁶⁵ has been investigated at the Karlsruhe research reactor using thermal neutron capture in Dy¹⁶⁴. The target was Dy₂O₃ enriched to 92.71% Dy¹⁶⁴. Neutrons were either monochromized by Bragg reflection from a lead crystal or transmitted through a bismuth single crystal filter. High-resolution measurements of the capture spectrum have been performed by means of a Ge(Li) 5-detector pair spectrometer and a Ge(Li) anti-Compton assembly. A large number of new lines has been observed. Cascade relationships were studied by using several techniques: a double coincidence apparatus with 4″ Ø×5″ NaI(Tl) detectors, a coincidence system containing a scintillation detector and a 34 cm³ Ge(Li)-diode as well as a two-parameter system involving the pair spectrometer (with NaI (Tl) as the primary detector) and a single 4″Ø×6″ NaI (Tl) counter. In the framework ofNilsson's model and simple microscopic pictures of vibrational states the results are consistent with the following spectroscopic interpretation: 0 keV, 7/2⁺[633]; 108.2 keV, 1/2^?[521]; 184.3 keV, 5/2″[512]; 533.5 keV, 5/2″ [523]; 538.6 keV, 7/2⁺[633] +Q₂₂; 570.3 keV, 5/2^?[512]+Q₂₂+1/2^?[510]; 573.6 keV, 3/2^? [521]+1/2^?[521]+Q₂₂; 1103.3 keV, 1/2^? [521]+Q₂₂+3/2^? [521]. For comparison preliminary results are given for the isotonic nucleus Yb¹⁶⁹.