Notiz zur quantitativen Bestimmung von Si-H- und Si-Si-Gruppen

Zusammenfassung Eine einfache und genaue Methode zur Bestimmung von Si-H- und Si-Si-Gruppen wird vorgeschlagen, die auf alkalischer Hydrolyse der Substanz in einem verschlossenen und evakuierten Kolben und AuswÄgen des dem entwickelten Wasserstoff entsprechenden Wasservolumens beruht. Bei H-Gehalten von 1–2% betrÄgt die Genauigkeit ± 0,03% (abs.).

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Note on the quantitative determination of Si-H- and Si-Si-groups

A simple, robust and surprisingly exact method for the quantitative determination of Si-H- or Si-Si-groups is based on alkaline hydrolysis of the Si-H- or Si-Si-containing substances in a sealed and evacuated vessel and weighing of the volume of water equivalent to the developed volume of hydrogen. The accuracy is ± 0.03% (abs.) with H contents of 1–2%.

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Herrn Prof. Dr. E. Asmus zum 60. Geburtstag gewidmet.     

1,8-bis(dimethylethyleneguanidino)naphthalene: tailoring the basicity of bisguanidine "proton sponges" by experiment and theory

1,8-bis(dimethylethyleneguanidino)naphthalene (DMEGN), the second example of a peralkyl guanidine "proton sponge" based on the 1,8-naphthalene backbone, was prepared and fully characterized. The crystal structure analysis of monoprotonated DMEGN reveals an unsymmetrical intramolecular hydrogen bridge. A decrease in the basicity with respect to the noncyclic parent 1,8-bis(tetramethylguanidino)naphthalene was found. Nevertheless, a new proton sponge provides a new crossbar in the ladder of highly basic neutral organic compounds. A detailed theoretical study of DMEGN and related cyclic guanidines explains this surprising experimental result. Homodesmotic reactions reveal that the intramolecular hydrogen bond contributes effectively 10 kcal/mol to proton affinity of DMEGN.     

Strukturen ladungsgestörter oder räumlich überfüllter Moleküle. 15. Tetracyanethen-Natrium-Dimethoxyethan

Structures of Charge-Perturbed or Sterically Overcrowded Molecules. 16. Tetracyanoethylene Sodium Dimethoxyethane The Single crystal structure of [(NC)₂C? C(CN)₂?·Na⊕(H₃CO? CH₂CH₂? OCH₃)]∞ reveals two formula units within the triclinic (P1 ) unit cell. The tetracyanoethylene radical anions are arranged along parallel double layers, which are shifted relative to each other, and in between which are interspersed the sodium counter cations and their dimethoxyethane ligands. The distances within the double layers amount to 300 pm and the ones between them to 385 pm. The six-fold coordinated Na⊕ centers are surrounded by four radical anions with contact distances Na…?N between 250 and 254 pm as well as by a twofold solvent ligand with Na…?O of 238 and 241 pm. Due to the electron transfer to the acceptor molecule, its (NC)₂C-halves twist by 8° and the bond lengths of the N?C? C subunits, bent by each 3°, are shortened up to 2 pm. The structural parameters are compared to those of the analogous potassium salt [TCNE^?K^⊕DME], of the dianion , of the sodium salts [(NC)₃C^?Na^⊕]∞ as well as [(NC)₂C? C(CHCH)₂? C(CN)₂^?Na^⊕]_∞ and, in addition, are discussed based on geometry-optimized MNDO calculations.     

Coordination of solvent molecules to VO(acac)<Subscript>2</Subscript> complexes in solution studied by hyperfine sublevel correlation spectroscopy and pulsed electron nuclear double resonance

Interactions and binding sites of the solvent molecules chloroform and ethanol to bis(acetylacetonate)oxovanadium(IV) (VO(acac)₂) complexes in (frozen) solutions have been investigated by pulsed electron nuclear double resonance, sum peak electron spin echo envelope modulation and hyperfine sublevel correlation spectroscopy. The experimental proton hyperfine coupling data of coordinating solvent molecules have been interpreted using quantum chemical calculations (density functional theory). Experimental and computed hyperfine couplings indicate that ethanol coordinates to vanadium in the equatorial plane of VO(acac)₂ and chloroform interacts via hydrogen bonding to oxygens of the acac ligands.     

Zur colorimetrischen Bestimmung von Rheniumspuren

Zusammenfassung Es wird gezeigt, daß mit Hilfe von Fuchsin eine colorimetrische Bestimmung von Rhenium in Mengen von 1–10 g mit einer Standardabweichung von 0,1 g möglich ist. Ein Abtrennungsverfahren, bestehend aus Sublimation des Rheniums und dessen Extraktion mit Tetraphenylarsoniumchlorid gestattet die Anwendung der colorimetrischen Methode zur Erfassung von Rheniumgehalten von 10^–1 bis 10^–4% in Mineralien und technischen Produkten.Herrn Prof. Geilmann und Herrn Prof. Bock danke ich für anregende Diskussionen. Herrn Prof. Strassmann und Herrn Dr. Herrmann bin ich für die Erlaubnis zur Benutzung der Hilfsmittel der radiochemischen Abteilung und für gegebene Ratschläge zu Dank verpflichtet.     

Characterisation of humic substances using atmospheric pressure chemical ionisation and electrospray ionisation mass spectrometry combined with size-exclusion chromatography

Humic substances were analysed by atmospheric pressure chemical ionisation (APCI) and electrospray ionisation (ESI) mass spectrometry in positive and negative modes. Using APCI the average m/z range of humic substances was reduced 5-fold compared to ESI. High-resolution time-of-flight mass spectrometry revealed the formation of multiply charged molecules in the ESI mode. Moreover, it was possible to obtain daughter ion mass spectra of humic substances by nanospray tandem mass spectrometry. The size-exclusion chromatography elution profile of humic substances was highly influenced by the pH of the analyte solution. By contrast, the pH had no significant influence on the observed mass spectra of humic substances.     

Cyclotomic units over finite fields

Let ζ be a primitivesp-th root of unity for a primep>2, and consider the group Ω(ζ) of cyclotomic units in the ringR(ζ)=ℒ[ζ+ζ^-1]. This paper deals with the image of Ω(ζ) in the unit group ofR(ζ)/qR(ζ), whereq is a prime ≠p. In particular, it obtains criteria for this image to be essentially everything, and a lower bound on the density of primesp (withq fixed) for which it cannot be. These results have a direct bearing on previous work about units in integral group rings for cyclic groups of orderpq. Work supported in part by an operating grant from NSERC (Canada).     

Almost block independence and bernoullicity of ℤ d -actions by automorphisms of compact abelian groups

Summary We prove that a ^d -action by automorphisms of a compact, abelian group is Bernoulli if and only if it has completely positive entropy. The key ingredients of the proof are the extension of certain notions of asymptotic block independence from -actions to ^d -action and their equivalence with Bernoullicity, and a surprisingly close link between one of these asymptotic block independence properties for ^d -actions by automorphisms of compact, abelian groups and the product formula for valuations on global fields.Oblatum 20-X-1994