Reactions of siliranes with elemental sulfur and with t-butyl mercaptan. Preparation of the 2,3-dithia-1-silacyclopentane ring system

The reaction of 1,1-dimethyl-trans-2,3,-bis(2′,2′-dimethylcyclopropylidene)-1-silirane with S₈ gives a mixture of four isomeric products derived from incorporation of one sulfur atom and a cyclopropylcarbinyl-to-butenyl type rearrangement. This silirane reacts with t-butyl mercaptan to give a product of mercaptan addition in which a cyclopropylcarbinyl-to-butenyl rearrangement also has occurred. Hexamethylsilirane reacts with S₈ to give 1,1,4,4,5,5-hexamethyl-2,3-dithia-1-silacyclopentane in high yield. These reactions are discussed in terms of free radical mechanisms.     

Reaktionen von komplexliganden : XIX. Einschiebung von inaminen in chrom-alkenylcarben- und chrom-aminocarber-bindungen

1-Diethylaminopropyne reacts with pentacarbonyl[methoxy(2,2-diphenylethenyl)carbene]chromium in a stereoselective way to give pentacarbonyl-[diethylamino-E-(2-methoxy-1-methyl-4,4-diphenyl-1,3-butadienyl)carbene]-chromium via insertion of the alkyne into the metal-carbene bond. The reaction of the ynamine with pentacarbonyl[methylamino(phenyl)carbene]chromium results in insertion of the alkyne and loss of carbon monoxide to give cis-tetracarbonyl[3-aza-1-methyl-2-phenyl-2-butenyl)diethylaminocarbene]-chromium. Its structure was established by oxidative degradation in an aqueous medium to give 2-benzoyl-N,N-diethylpropanamide and finally confirmed by an X-ray analysis. The new compounds are characterized spectroscopically.     

The activation energy of the skeletal isomerization in the radical cations of toluene and cycloheptatriene by mass spectrometry of their 2-phenylethyl derivatives

The Unimolecular mass spectrometric fragmentations of the molecular ions of 1,3-diphenylpropane, 1-(7-cycloheptatrienyl)-2-phenylethane and the 1-phenyl-2-tolylethanes and their [d₅]phenyl analogues have been investigated by metastable ion techniques and measurements of ionization and appearance energies. By comparing the formation of [C₇H₇]⁺, [C₇H₈]⁺?, [C₈H₈]⁺? and [C₈H₉]⁺ it is shown that the molecular ions of the four diaryl isomers do not undergo ring expansion reactions of the aromatic nuclei prior to these fragmentations. Conversely, the molecular ions of the cycloheptatrienyl isomer suffer in part a contraction of the 7-membered ring. From these results and from the measured ionization and appearance energies lower limits to the activation energies of these skeletal isomerizations have been estimated yielding E > 33±5 kcal mol^?1 formonoalkylbenzene, E > 20 2±5 kc mol^?1 for 7-alkylcycloheptatriene and E > 40±5 kcal mol^?1 for dialkylvbenzene positive radical ions. Upper limits can be deduced from literature evidence yielding E < 45 kcal mol^?1 for monoalkylbenzene and E < 53 kcal 4mol^?1 for dialkylbenzene positive radical ions. The activation energy thus estimated for monoalkylbenzene is in excellent agreement with the recently calculated value(s) for the toluene ion.     

Biosynthesis of 4-methylproline in cyanobacteria: cloning of nosE and nosF genes and biochemical characterization of the encoded dehydrogenase and reductase activities

The biosynthesis of the unusual amino acid 4-methylproline in the Nostoc genus of cyanobacteria was investigated on the genetic and enzymatic level. Two genes involved in the biosynthesis were cloned and the corresponding enzymes, a zinc-dependent long-chain dehydrogenase and a Delta(1)-pyrroline-5-carboxylic acid (P5C) reductase homologue, were overexpressed in Escherichia coli and biochemically characterized. Putative substrates were synthesized to test enzyme substrate specificities, and deuterium labeling studies were carried out to reveal the stereospecificities of the enzymatic reactions with respect to the substrates as well as to the coenzymes.     

Glow discharge mass spectrometry — A versatile tool for elemental analysis

Summary Among recent MS techniques for elemental analysis, Glow Discharge Mass Spectrometry (GDMS) covers the field of direct analysis of conducting and semiconducting solids. In GDMS, a glow discharge in a working gas — usually Ar — at reduced pressure serves to atomize a solid sample by cathodic sputtering and to ionize the vapourized atoms. Ions are separated according to mass by a quadrupole filter (with low mass resolution) or a double focusing device (with high mass resolution). Use of a working gas implies the appearance of spectral interferences by molecular ions. Analysis may be impeded by these interferences, even in the case of high mass resolution. GDMS shows convincing analytical performance. Detection limits in the low ng/g region and even below can easily be realized. Precision is normally in the low percentage region, and a dynamic region of about nine orders of magnitude may be covered. Matrix effects are of no significant influence, and elemental sensitivities are within one order of magnitude. Semiquantitative analysis without standards is possible with limited accuracy, which is of considerable practical interest in the sub-microtrace region. Application experiences have mainly been gathered in analysis of very pure materials and semiconductors. GDMS has also been applied successfully for analytical characterization of technical surface layers.     

Skyrmion strings and the anomalous Hall effect in CrO2

Topological (or singularity point) defects are thought to play a crucial role in the phase transitions of 3D spin systems, as they do in such 2D systems as the XY model. In double-exchange ferromagnets the conduction electrons are strongly coupled with core spins through Hund's rule, and, in the presence of a nontrivial spin texture, acquire a Berry phase contribution to the anomalous Hall effect. We combine Hall effect and magnetization data on CrO2 with a thermodynamical scaling hypothesis to confirm that the critical behavior of the topological-spin-defect density is consistent with that of the heat capacity. This analysis is the first experimental confirmation of the topological character of critical fluctuations.