Inter- and intra-annular proton exchange in gaseous benzylbenzenium ions (protonated diphenylmethane)

Two distinct proton exchange reactions occur in metastable gaseous benzylbenzenium ions, generated by isobutane chemical ionization of diphenylmethane and four deuterium-labelled analogues. Whereas the proton ring-walk at the benzenium moiety is fast giving rise to a completely random intraannular proton exchange, the interannular proton exchange is surprisingly slow and competes with the elimination of benzene. A kinetic isotope effect of k_H/k_D= 5 has been determined for the interannular proton transfer, and a particularly high energy barrier of 50–75 kJ mol^?1 has been estimated. These observations are attributed to steric restrictions of the ring-to-ring proton transfer in benzylbenzenium ions and contrasted to the fast interannular proton exchange in the higher homologues.     

VNCl2(Pyridin)2 Synthese,IR-Spektrum und Kristallstruktur

VNCl₂(Pyridine)₂; Synthesis, I. R. Spectrum, and Crystal Structure VNCl₂(Pyridine)₂ is formed from the cyclothiazeno-vanadium(IV) complex [VCl(N₃S₂)(Pyridine)₂]₂ · 2 CH₂Cl₂ in boiling toluene in form of brown-red, hydrolysis sensitive crystal. It was characterized by its I.R. spectrum and an X-ray crystal structure determination. VNCl₂(Pyridine)₂crystallizes in the orthorhombic space group Pccn with four formula units per unit cell (668 observed independent reflexions, R = 0.055). Lattice constants: a = 1550, b = 924, c = 832 pm. Monomer molecules are situated on twofold rotation axes. They are stacked along the V?N axis to form columns V?N…V. The short VN bond of 160 pm corresponds to a triple bond, whereas the V…N distance of 256 pm indicates a weak interaction. The V? N(Pyridine) and V? Cl bond lengths are 213.0 and 233.5 pm, respectively.     

Optisch aktive übergangsmetall-komplexe XX. Optisch aktive cyclopentadienyl-perfluoropropyl-kobalt-komplexe mit zweizähnigen schiff-basen

In the reaction of C₅H₅ Co(C₃F₇)(CO)I with the Schiff base NN′, derived from S-(-)-?-phenylethylamine and pyridine carbaldehyde-2, the salt [C₅H₅Co(C₃F₇)NN′]⁺ I^? (Ia,b) is formed, which can be transformed to [C₅H₅ Co(C₃F₇)NN′]⁺ PF₆^? (IIa,b). The sodium salt Na⁺ [NN″]^? of the Schiff base, derived from S-(-)-α-phenylethylamine and pyrrol carbaldehyde-2, in the reaction with C₅H₅ C0(C₃F₇)(CO)I yields the neutral complex C₅H₅ Co(C₃F₇)NN″ (IIIa,b). The diastereoisomeric pairs IIa,b and IIIa,b are separated by fractional crystallisation and chromatography respectively into the optically pure components which differ in their ¹H NMR spectra. The IR, UV, CD, mass spectra and optical rotations of the new compounds IIa, IIb, IIIa and IIIb are compared.     

Analysis of the disaccharides derived from hyaluronic acid and chondroitin sulfate by capillary electrophoresis with sample stacking

CE conditions for monitoring the unsaturated disaccharides of hyaluronic acid (di-HA) and chondroitin sulfate (di-CS) using an alkaline tetraborate buffer, electrokinetic sample injection, and UV absorption detection at 232 nm are reported. Separations were performed in an uncoated fused-silica capillary having reversed polarity and reversed electroosmosis generated with the addition of CTAB to the buffer. The influence of various separation parameters, including the concentration of CTAB, buffer pH, concentration of tetraborate, and applied voltage, on the resolution of the two disaccharides was investigated. Baseline separation was obtained with 25 mM tetraborate at pH 10.0 and having 0.05 mM CTAB. Chloride and phosphate in the sample are beneficial for the stacking of the disaccharides, with di-HA forming a much sharper peak than di-CS. Using samples prepared in 25 mM Tris-HCl (pH 7.5) and electrokinetic injection at the cathode at -10 kV for 40 s, linear relationships between the corrected peak area and the concentration of the disaccharides have been found in the ranges of 1.0-400.0 and 0.1-1.0 microg/mL (0.2-1.0 microg/mL for di-CS), with correlation coefficients being >0.9933 in all cases. The RSDs of detection times and corrected peak areas were between 1.13-1.24 and 1.57-2.13%, respectively. Applied to human serum samples that were prepared by ethanol precipitation and depolymerization of the two polysaccharides with chondroitinase ABC reveals comigration of endogenous compounds with di-HA and a sample-dependent detection time. The di-HA content in the serum sample can be estimated via subtraction of the blank peak that is obtained without enzymatic hydrolysis.     

Trace analysis of rapamycin in human blood by micellar electrokinetic chromatography

A capillary electrophoretic method with UV detection at 278 nm has been developed for analysis of the immunosuppressant rapamycin (sirolimus) in human blood at low microgram per liter levels. Separation has been achieved in an acidic carrier electrolyte containing sodium dodecylsulfate and 30% (v/v) acetonitrile. For sample clean-up and preconcentration, an off-line solid-phase extraction step using a silica-based reversed-phase material and an on-capillary focussing technique were employed. The latter allows the injection of increased sample volumes without excessive band broadening. Although this new method is less sensitive than existing liquid chromatographic procedures combined with mass spectrometry, it is fully suited to routine analysis of rapamycin in blood from patients treated with this drug. Last but not least the low costs make it an attractive alternative to established methods.     

N-heterocyclic carbenes as ligands in high-valent molybdenum and tungsten complexes

Oxometal complexes of molybdenum and tungsten in high oxidation states from stable adducts with 1,3-dimethylimidazoline-2-ylidene (L) 1. The first ‘carbene’ complexes of molybdenum(VI) [MoO₂Cl(L)₃]Cl (3a) and tungsten(VI) WO₂Cl₂(L)₂ (4b) are reported.     

Gradient extremals and valley floor bifurcations on potential energy surfaces

Gradient extremals are curves in configuration space denned by the condition that the gradient of the potential energy is an eigenvector of the Hessian matrix. Solutions of a corresponding equation go along a valley floor or along a crest of a ridge, if the norm of the gradient is a minimum, and along a cirque or a cliff or a flank of one of the two if the gradient norm is a maximum. Properties of gradient extremals are discussed for simple 2D model surfaces including the problem of valley bifurcations.