Neue Rheniumkomplexe mit Trichalkogenido- und Tetrachalkogenido-Chelatliganden

New Rhenium Complexes Containing Trichalcogenido and Tetrachalcogenido Chelate Ligands The reactions of Cp*ReCl₄ with polychalcogenide salts such as Na₂S₄ or (NEt₄)₂Se₆ lead initially to the violet trichalcogenido chelate complexes Cp*ReCl₂(E₃) (E = S ( 3a ), Se ( 3b )) which, due to their functional chloro ligands, can be used as intermediates for further reactions. Upon hydrolysis in moist solvents or aminolysis with tert. butylamine 3a, b are converted into the tetrachalcogenido chelate complexes Cp*Re(O)(E₄) (E = S ( 4a ), Se ( 4b )) and Cp*Re(N^tBu)(E₄) (E = S ( 5a ), Se ( 5b )), respectively. X-Ray structure analyses were carried out for the three mononuclear cyclo-oligoselenido compounds 3b–5b . It appears that the size of the Se^2?_n chelate ring (n = 3 or 4) essentially depends on steric factors within the coordination sphere of rhenium.     

Alkaline Earth Transition Metal Antimonides AT4Sb12 (A = Ca,Sr, Ba; T = Fe,Ru, Os) with LaFe4P12-Structure

The title compounds were prepared by reaction of CaSb₂, SrSb₂, or BaSb₃ with the transition metals and antimony in sealed silica tubes. They crystallize with the cubic LaFe₄P₁₂-structure, which was refined from single-crystal X-ray data of CaFe₄Sb₁₂, SrRu₄Sb₁₂, and BaRu₄Sb₁₂ to residuals of R = 0.014, 0.016, and 0.014, respectively. The thermal parameters of the alkaline earth ions increase with decreasing ionic size. The Sb? Sb distances are greater in the iron compound than they are in the two ruthenium compounds. This is rationalized to be due to a larger portion of electrons in antibonding Sb? Sb states in the iron compound.     

Characterization of Carbohydrates in Paper and Paper Pulps Using Anion Exchange Chromatography and Principal Component Analysis

In the course of this investigation, a method for the characterization and differentiation of paper pulps was developed. After hydrolyzation of the papers and the respective raw pulps with trifluoroacetic acid, the hydrolyzates were analyzed with respect to their carbohydrate composition using ion exchange chromatography. The variations in carbohydrate composition mainly arise from the various hemicelluloses of the papers and pulps. The chromatographic results were then further processed using principal component analysis which allows correlating the various papers to different pulp materials.     

Spectrophotometric determination of total phenolics by solvent extraction and sorbent extraction optosensing using flow injection methodology

Flow injection analysis (FIA) procedures for the Spectrophotometric determination of phenol involving in-line concentration by solvent and sorbent extraction have been developed. The imine product formed in the reaction between phenol and 4-aminoantipyrine (4-AAP) is either extracted into chloroform (solvent extraction) or is temporarily retained on C₁₈-modified silica material contained in a microcolumn (sorbent extraction). In the latter case two variants of detection have been used namely the Spectrophotometric measurement of the methanolic eluent containing the concentrated dye and at-column optosensing of the retained reaction product followed by methanol elution to maintain reversibility of the process. In the solvent extraction procedure a 10-fold increase of sensitivity compared to the common FIA method without extraction is achieved but no corresponding improvement in detectability is observed. Under optimized conditions the detection limit amounts to 8 μg l⁻¹. Using sorbent extraction methodology, high concentration factors can be obtained when large sample volumes are used. The only limitation in getting correspondingly lower detection limits are an increasingly high and variable blank value with sampling volume. The detection limits obtained for measurement of the absorbance in the eluent and on-column optosensing are 11 μg l⁻¹ and 0.4 μg l⁻¹, respectively. A study of the extractability of various phenol derivates using both solvent and sorbent extraction revealed lower relative response rates compared to the FIA method without extraction. Phenolics that possess an additional acidic group are present in ionized form at the high pH of the assay and are not extractable at all.     

The Role of Binary and Many-centre Molecular Interactions in Spin Crossover in the Solid State. Part I. Equation for Free Energy

Summary. A formalism has been developed that describes spin crossover equilibrium in the solid state by taking into account the effects of n nearest neighbours of a given molecule on its partition function. In this way binary and many-body interactions of the order n + 1 are included into the theoretical model and represented by non-ideality parameters connected with the splitting of free energy levels. Binary interactions are characterised by the main splittings whereas higher order interactions manifest themselves in asymmetries of splittings within multiplets. The contribution of molecular interactions can also be written in terms of formal excess free energies of the second, third, fourth and higher orders. Simple relationships between excess free energies and parameters of multiplets have been found for binary, ternary and quaternary interactions. This formalism is reduced to that of the model of binary interactions when effects of surroundings are additive leading to equidistant free energy multiplets. Higher order interactions may cause an abrupt spin crossover but in a limited range of compositions around the transition point. The regression of experimental transition curves of one-step spin crossover may yield estimates of excess energies up to the fifth order.     

Rotational spectrum, potential energy surface, and bound states of the weakly bound complex He-N2O

Pure rotational transitions of the weakly bound complex He-N(2)O and three minor isotopomers (He-(14)N(15)NO, He-(15)N(14)NO, and He-(15)N(15)NO) were measured in the frequency region from 6 to 20 GHz. Predictions for the microwave transition frequencies were based on the infrared work by Tang and McKellar [J. Chem. Phys. 117, 2586 (2002)]. In the case of (14)N containing isotopomers, nuclear quadrupole hyperfine structure of the rotational transitions was observed and analyzed. The resulting spectroscopic parameters were used to determine geometrical and dynamical information about the complex. An ab initio potential energy surface was calculated at the coupled cluster level of theory with single and double excitations and perturbative inclusion of triple excitations. This surface was constructed using the augmented correlation consistent polarized valence triple zeta basis set for all atoms with the inclusion of bond functions for the van der Waals bond. Bound state calculations were done to determine the energies of low-lying rovibrational levels that are supported by the potential energy surface. The resulting transition energies agree with the experimental values to 1% or better.     

Lanthanoid-nickel-phosphides with ThCr2Si2-type structure

The new compounds YNi₂P₂ and LnNi₂P₂ (Ln = La, Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm) were prépared by sintering the elemental components in silica tubes. Well-developed crystals were obtained using tin as a flux. They crystallize with the ThCr₂Si₂ (CeGa₂Al₂)-type structure which was refined from single-crystal X-ray data for EuNi₂P₂ to a conventional R value of 0.049 for 118 unique structure factors. While the P atoms in formally isotypic EuCo₂P₂ are isolated from each other, they form pairs in EuNi₂P₂. This results in a different $\text{c}\text{a}$ ratio and an entirely different bonding situation. A comparison of cell volumes shows that Eu in EuNi₂P₂ has an intermediate valence.     

Synthesis of 5-Substituted 1,3-Dimethylpyrazolo[4,3-e][1,2,4]triazines

A novel method for the synthesis of a new series of 5-substituted 1,3-dimethyl pyrazolo[4,3-e][1,2,4]triazines is described. The new synthetic strategy is based on the classical Bischler 1,2,4-benzotriazine synthesis. This approach involves the preparation of 5-hydrazinopyrazole from 5-chloro-1,3-dimethyl-4-nitropyrazole followed by acylation and nitro group reduction to form the corresponding 4-amino-3-(acylhydrazino)pyrazoles. Intramolecular oxidative cyclization of the latter derivatives, using polyphosphoric acid, produced the respective target pyrazolotriazines.     

On the underestimated influence of synthetic conditions in solid ionic conductors

The development of high-performance inorganic solid electrolytes is central to achieving high-energy- density solid-state batteries. Whereas these solid-state materials are often prepared via classic solid-state syntheses, recent efforts in the community have shown that mechanochemical reactions, solution syntheses, microwave syntheses, and various post-synthetic heat treatment routines can drastically affect the structure and microstructure, and with it, the transport properties of the materials. On the one hand, these are important considerations for the upscaling of a materials processing route for industrial applications and industrial production. On the other hand, it shows that the influence of the different syntheses on the materials'' properties is neither well understood fundamentally nor broadly internalized well. Here we aim to review the recent efforts on understanding the influence of the synthetic procedure on the synthesis – (micro)structure – transport correlations in superionic conductors. Our aim is to provide the field of solid-state research a direction for future efforts to better understand current materials properties based on synthetic routes, rather than having an overly simplistic idea of any given composition having an intrinsic conductivity. We hope this review will shed light on the underestimated influence of synthesis on the transport properties of solid electrolytes toward the design of syntheses of future solid electrolytes and help guide industrial efforts of known materials.

Influence of synthesis and processing on the nature of ultimate product and the ionic transport properties of superionic conductors.     

Synthese und Reaktionen von Bicyclo[6.4.0]dodecan-3-carbonsäure-Derivaten

Synthesis and Reactions of the Bicyclo[6.4.0]dodecane-3-carboxylic Acid Derivatives The synthesis and some consecutive reactions of the compounds 5-8 , derivatives of bicyclo[6.4.0]dodecane-3-carboxylic acid ( 1 ), are described. The esters 7 and 8 can be obtained by Baeyer-Villiger oxidation of 2-hydroxy-8-methyltricyclo[7.3.1.0^2,7]tridecan-13-one ( 4 ) and subsequent hydrolysis of the lactone 5 . The structure and configuration of these compounds has been evaluated by spectroscopic techniques (mainly 2D-NMR methods). The formation of 7 via 1,2-H shift and subsequent isomerization to 8 has been studied. The esters 11 and 13 are formed stereospecifically from 7 and 8 .