Dehydration of Alkanones by Bare FeO+ Involves the ω/(ω − 1) Positions: Exclusion of Iron Carbenes as Intermediates. Preliminary Communication

Fourier-transform ion-cyclotron-resonance (FTICR) mass spectrometry has been used to uncover the mechanisms by which FeO⁺ dehydrates heptan-4-one ( 5a ) and nonan-5-one ( 6a ) in the gas phase. The study of isotopomeric ketones provides evidence that H₂O loss is not due to a 1,1-elimination, thus ruling out the intermediacy of high-valent iron-carbene species. Rather, H₂O is generated in a formal 1,2-elimination involving the ω/ω ? 1 positions of the alkyl chain (‘remote C? H bond activation’). In the consecutive alkene/H₂O elimination, the olefins (ethylene from 5a and propene from 6a ) originate from the terminal part of one alkyl chain, and the H-atom is transferred to the FeO⁺ moiety in the course of this process, builds up together with an H-atom from the ω/ω-1 position of the other alkyl chain the H₂O molecule. In either case, the O-atom of H₂O is provided by the FeO⁺ species.     

Observation of the ND4 Schüler band in a neutralized ion beam experiment

The emission of the ND₄ Schüler band was observed after neutralization of a mass-selected ND ₄ ⁺ ion beam. Thus the assignment of this band to the ammonium radical was confirmed. The lifetime of the upper state (3p ² F ₂) was determined to be 4.2 ns, which is much shorter than ab initio values of the radiative lifetime, showing that this state decays predominantly by predissociation. The Schuster band was not observed, neither after neutralization of ND ₄ ⁺ , nor of ND ₃ ⁺ .     

Relativistic all electron configuration interaction calculation of ground and excited states of the gold hydride molecule

We present relativistic configuration interaction calculations with the spin-free no-pair hamiltonian on the gold hydride molecule, treating the ground state as well as the eleven lowest excited states. The calculations provide a picture of the bonding in theX ¹Σ⁺ ground state consistent with previous work on this species using four-component spinors: compared to non-relativistic calculations, the dipole moment is reduced by a factor of two, hybridization (and thus participation ofd orbitals at the bonding) is greatly enhanced, the bond length is shortened by 20 pm, and the dissociation energy is increased by 50%. Comparison of the spin-averaged potential curves of the excited states with experiment suggests a reinterpretation of theC ¹Σ⁺ as the 0⁺ fine structure component of 2³Π and the prediction of a weakly bound³Σ⁺ state with weak transitions to the ground state in the range of 2.9–3.1 eV.     

Theoretical treatment of the spectrophotometric titration of bivalent cations with complexon-iii and metal-specific indicators

It was derived theoretically that a sharp end-point of this spectrophotometrical titration is defined, in order of importance, by: 1. *K_C ? *K_I (numerically speaking, log$\text{*K}{}_{\mathrm{C}}\text{*K}{}_{\mathrm{I}}$ should be at least 4); 2. *K_I being large (numerically e.g. 10⁴-10⁵); this is already reached by choosing a high pH; 3. it being low; 4. m_t being as high as possible.     

The complete 51V MAS NMR spectrum of surface vanadia nanoparticles on anatase (TiO2): vanadia surface structure of a DeNOx catalyst

The first observations of the complete manifold of spinning sidebands (ssbs) including both the central and satellite transitions in (51)V MAS NMR spectra of surface vanadia nanoparticles on titania in DeNO(x) catalysts are presented. (51)V quadrupole coupling and chemical shift anisotropy parameters for the dominating vanadia structure are determined from (51)V MAS NMR spectra recorded at 9.4 and 14.1 T. Based on correlations previously established between (51)V NMR parameters and crystal structure data for inorganic vanadates, the NMR data are consistent with vanadium in a distorted octahedral oxygen coordination environment for the so-called strongly bonded vanadia species on the surface. The investigation includes two vanadia-titania model catalysts and six industrial-type DeNO(x) catalysts.     

Synthesis and Transformation of Methyl 2‐(6‐Hydroxy‐2‐phenylpyrimidin‐4‐yl)acetate: Simple Preparation of Pyrimidines with Heterocyclic Substituents

A simple and efficient synthesis of four new substituted pyrimidines, compounds 9a – d , from the title compound 3 is described. Conversion of 3 to methyl (E)‐3‐(dimethylamino)‐2‐(6‐methoxy‐2‐phenylpyrimidin‐4‐yl)prop‐2‐enoate ( 4 ), followed by condensation with various dinucleophiles according to the ‘enaminone methodology’, afforded the target compounds 9 in medium‐to‐good yields.     

Synthese und Charakterisierung funktionalisierter β‐Hydroxydithiozimtsäuren und deren Ester. Komplexchemisches Verhalten gegenüber Nickel(II), Palladium(II) und Platin(II)

Synthesis and Analytical Characterization of Functionalized β‐Hydroxydithiocinnamic Acids and their Esters. Complex Chemistry towards Nickel(II), Palladium(II), and Platin(II) Starting from silyl‐protected 4‐hydroxy acetophenone ( 1 ) the 1,1‐ethenedihiolato complexes 3 – 5 were synthesised using carbon disulfide and potassium‐tert‐butylate as a base. After being deprotected, the resulting 4‐hydroxy‐substituted complexes 6 – 8 were esterified with DL‐α‐lipoic acid to obtain the compounds 9 – 11 . The resulting complexes were characterized using NMR spectroscopy, mass spectrometry and IR spectroscopy. 3‐substituted β‐hydroxydithiocinnamic acid methyl ester ( 12 ) was obtained via an analogous path of reaction using silyl‐protected 3‐hydroxy acetophenone ( 2 ), carbon disulfide and methyl iodide. After removing of the silyl group the resulting hydroxy group was esterified with DL‐α‐lipoic acid. Using the dithioacid ester 14 as a ligand the Ni^II ( 15 ), Pd^II ( 16 ) and Pt^II ( 17 ) [O,S] complexes were obtained.     

An experimental study of chromatographic dynamics in open and packed non-cylindrical conduits

A systematic investigation of the influence of the perimeter shape of open and particle packed fused silica capillaries on chromatographic properties such as resistance to flow and dispersion of solutes propelled through these channels has been conducted. Verifications of these uncommon experiments with existing theoretical treatments are presented and the insights transferred to a novel polymer chip design with integrated facilities for complex separations. A comparison of the chromatographic performance of a real life proteomics sample on this chip with a capillary column of "similar" dimensions is presented.     

Determination of organophosphorus, triazine and 2,6-dinitroaniline pesticides in aqueous samples via solid-phase microextraction (SPME) and gas chromatography with nitrogen-phosphorus detection

Solid-phase microextraction (SPME) represents a very simple and rapid method for the extraction of organophosphorus, triazine and 2,6-dinitroaniline pesticides from aqueous samples without making use of any solvents. The same fiber can be used repeatedly. Moreover, a sample volume as small as 3 mL can be employed with no loss in sensitivity. 34 compounds have been extracted from aqueous samples by SPME using a 85 m polyacrylate fiber. For organophosphorus pesticides, a 100 m polydimethylsiloxane fiber has been used additionally for comparison. The fibers were directly introduced into the heated split/splitless injector of the gas chromatograph and determined using a nitrogen-phosphorus detector. The method was evaluated with respect to the limit of detection (LOD), linearity and precision. The limit of detection (LOD) depends on the compound and varies from 0.005–0.09 g/L. The method is linear over at least three orders of magnitude with coefficients of correlation usually >0.999. For triazines and 2,6-dinitroanilines the coefficient of variation (precision) is <8% while for organophosphorus compounds it may reach values up to 18% (however, if the latter compounds are extracted using the polydimethylsiloxane phase considerably higher precision is achieved). The partitioning of the analyte between the aqueous phase and the polymeric phase depends on the hydrophobicity of the compound as expressed by the octanol/water partitioning coefficient (P_ow). For triazines it was shown that there is a linear dependence of the logarithm of the analyte response on the log(P_ow) i.e. the higher the hydrophobicity, the higher the affinity of the analytes to the polymeric phase of the fiber and the higher the response. Salt addition has a strong effect on the extraction efficiency. This effect increases with decreasing hydrophobicity (increasing polarity) of the compound. The triazines ametryn, atrazine, propazine, simazine and simetryn have been identified in a ground water well sample by SPMEGC/NPD.     

Electromagnetic fission of238U at 600 and 1000 MeV per nucleon

Electromagnetic fission of²³⁸U projectiles at E/A =600 and 1000 MeV was studied with the ALADIN spectrometer at the heavy-ion synchrotron SIS. Seven different targets (Be, C, Al, Cu, In, Au and U) were used. By considering only those fission events where the two charges added up to 92, most of the nuclear interactions were excluded. The nuclear contributions to the measured fission cross sections were determined by extrapolating from beryllium to the heavier targets with the concept of factorization. The obtained cross sections for electromagnetic fission are well reproduced by extended Weizsäcker-Williams calculations which include E1 and E2 excitations. The asymmetry of the fission fragments' charge distribution gives evidence for the excitation of the double giant-dipole resonance in uranium.Communicated by V. Metag