The chemistry of piperidines—II: The electron-impact-induced fragmentation of 3-AZA-3-methylbicyclo[3,3,1]nonanes

The mass spectra of three series of stereoisomeric 3-aza-3-methyl-6-cycloalkylaminobicyclo[3,3,1]nonan-9-ols and related compounds including deaza analogues are reported and discussed. The spectra of some of the isomers differ characteristically and can be used to assign their configurations.     

Phosphaadamantanes as ligands for palladium catalyzed cross-coupling chemistry: library synthesis, characterization, and screening in the Suzuki coupling of alkyl halides and tosylates containing beta-hydrogens with boronic acids and alkylboranes

A 15-member library of phosphaadamantane ligands has been prepared via P-arylation of 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phosphaadamantane. Screening of this tertiary phosphine collection has allowed for the rapid determination of the most suitable ligand, specifically 1,3,5,7-tetramethyl-6-(2,4-dimethoxyphenyl)-2,4,8-trioxa-6-phosphaadamantane, for facilitating Suzuki-type couplings of alkyl halides or tosylates containing beta-hydrogens with either boronic acids or alkylboranes.     

The chemistry of piperidines—I : 3-Azabicyclo[3.3.1]nonanes

The reaction of pyrrolidine, piperidine and morpholine enamines of 1-methyl-4-piperidone with acraldehyde is found to be a convenient route to 3-aza-3-methyl-6-cycloalkylaminobicyclo[3.3.1]-nonan-9-ones. In each case two difficultly separable ketones are obtained which on reduction give mixtures of isomeric alcohols. The alcohols are separated and their stereochemistries are determined from their physical and chemical properties.     

Adsorptions-kinetik von Einzelschichten von Eieralbumin

Ohne Zusammenfassung     

An alternating pi-stacked bisdithiazolyl radical conductor

A general synthetic route to the resonance-stabilized pyrazine-bridged bisdithiazolyl framework, involving the reductive deprotection of 2,6-diaminopyrazine-bisthiocyanate and cyclization with thionyl chloride, has been developed. An N-methyl bisdithiazolyl radical, 4-methyl-4H-bis[1,2,3]dithiazolo[4,5-b:5',4'-e]pyrazin-3-yl, has been prepared and characterized in solution by electron paramagnetic resonance spectroscopy and cyclic voltammetry. Its crystal structure has been determined at several temperatures. At 295 K, the structure belongs to the space group Cmca and consists of evenly spaced radicals pi-stacked in an alternating ABABAB fashion along the x-direction. At 123 K, the space group symmetry is lowered by loss of C-centering to Pccn, so that the radicals are no longer evenly spaced along the pi-stack. At 88 K, a further lowering of space group symmetry to P21/c is observed. Extended Hückel Theory band structure calculations indicate a progressive opening of a band gap at the Fermi level in the low-temperature structures. Magnetic susceptibility measurements over the range 4-300 K reveal essentially diamagnetic behavior below 120 K. Variable-temperature single-crystal conductivity (sigma) measurements indicate that the conductivity is activated, even at room temperature, with a room-temperature value sigma RT=0.001 S cm-1 and a thermal activation energy Eact=0.19 eV. Under an applied pressure of 5 GPa, sigma RT is increased by 3 orders of magnitude, but the conductivity remains activated, with Eact being lowered to 0.11 eV at 5.5 GPa.     

Laser smoothing of sub-micron grooves in hydroxyl-rich fused silica

Nano- to micrometer-sized surface defects on UV-grade fused silica surfaces are known to be effectively smoothed through the use of high-temperature localized CO₂ laser heating, thereby enhancing optical properties. However, the details of the mass transport and the effect of hydroxyl content on the laser smoothing of defective silica at sub-micron length scales are still not completely understood. In this study, we examine the morphological evolution of sub-micron, dry-etched periodic surface structures on type II and type III SiO₂ substrates under 10.6 μm CO₂ laser irradiation using atomic force microscopy (AFM). In situ thermal imaging was used to map the transient temperature field across the heated region, allowing assessment of the T-dependent mass transport mechanisms under different laser-heating conditions. Computational fluid dynamics simulations correlated well with experimental results, and showed that for large effective capillary numbers (N_c > 2), surface diffusion is negligible and smoothing is dictated by capillary action, despite the relatively small spatial scales studied here. Extracted viscosity values over 1700-2000 K were higher than the predicted bulk values, but were consistent with the surface depletion of OH groups, which was confirmed using confocal Raman microscopy.     

Metal complexes of bridging neutral radical ligands: pymDTDA and pymDSDA

Metal complexes of the 4-(2'-pyrimidyl)-1,2,3,5-dithiadiazolyl (pymDTDA) neutral radical ligand and its selenium analogue (pymDSDA) are presented. The following series of metal ions has been studied using M(hfac)(2) as the coordination fragment of choice (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonato): Mn(II), Co(II), Ni(II), and Zn(II). The binuclear cobalt and nickel complexes of pymDTDA both exhibit ferromagnetic (FM) coupling between the unpaired electrons on the ligand and the metal ion, while the binuclear zinc complex of pymDTDA is presented as a comparative example incorporating a diamagnetic metal ion. The binuclear manganese complex of pymDTDA, reported in a preliminary communication, is compared to the pymDSDA analogue, and new insight into the magnetic behavior reveals that intermolecular magnetic coupling, mediated by chalcogen-oxygen contacts, gives rise to a significant increase in the χT product at low temperature. Surprisingly, the binuclear nickel complex of pymDSDA forms dimers in the solid state, as do the mononuclear complexes of cobalt and nickel with pymDTDA. In addition, mixed mononuclear/binuclear complexes of Mn- and Zn(pymDTDA) have been identified.