Dreiphasige Emulsionen

Ohne Zusammenfassung     

Diethyl-2,2′-bipyridyl-palladium(II), a case for the study of combination vs. disproportionation products.

Diethyl-2,2′-bipyridyl-palladium(II) is synthesized and its decomposition reactions in absence and presence of methyl acrylate are compared with those of the corresponding nickel and platinum complexes. Depending on the reaction conditions either CC-coupling or disproportionation can be induced.     

Komplexkatalyse: XXV. 31P-NMR-spektroskopische charakterisierung der anti- und syn-struktur von C3-substituierten η3-allylbis(triarylphosphit)-nickel(II)-hexafluorophosphat-komplexen und der mechanismus der durch [C3H5Ni(P(OPh)3)2]PF6 katalysierten 1,4-trans-polymerisation des butadiens

The reaction of the η₃-allylbis(triarylphosphite)nickel(II) complexes with butadiene under chain propagation to give the polybutadienyl complex, [3-RC₃H₄Ni(P(OAr)₃)₂]PF₆, was monitored by ³¹P NMR spectroscopy. In the case of the triphenylphosphite complex both the anti- and the syn-configuration could be identified by means of their different AB spectra. The anti-syn isomerization, the higher reactivity of the thermodynamically more stable syn-form, and the formation of the anti-structure as a result of each individual butadiene insertion step was also proved. From these observations an experimentally well-grounded mechanism of the trans regulation with the anti-syn isomerization as the rate-determining step could be derived for the first time.     

Towards quantitative catalytic lignin depolymerization

The products of base-catalyzed liquid-phase hydrolysis of lignin depend markedly on the operating conditions. By varying temperature, pressure, catalyst concentration, and residence time, the yield of monomers and oligomers from depolymerized lignin can be adjusted. It is shown that monomers of phenolic derivatives are the only primary products of base-catalyzed hydrolysis and that oligomers form as secondary products. Oligomerization and polymerization of these highly reactive products, however, limit the amount of obtainable product oil containing low-molecular-weight phenolic products. Therefore, inhibition of concurrent oligomerization and polymerization reactions during hydrothermal lignin depolymerization is important to enhance product yields. Applying boric acid as a capping agent to suppress addition and condensation reactions of initially formed products is presented as a successful approach in this direction. Combination of base-catalyzed lignin hydrolysis with addition of boric acid protecting agent shifts the product distribution to lower molecular weight compounds and increases product yields beyond 85%.     

Intra-operative optical diagnostics with vibrational spectroscopy

Established methods for characterization of tissue and diagnostics, for example histochemistry, magnetic resonance imaging (MRI), X-ray tomography, or positron emission tomography (PET), are mostly not suitable for intra-operative use. However, there is a clear need for an intra-operative diagnostics especially to identify the borderline between normal and tumor tissue. Currently, vibrational spectroscopy techniques (both Raman and infrared) complement the standard methods for tissue diagnostics. Vibrational spectroscopy has the potential for intra-operative use, because it can provide a biochemically based profile of tissue in real time and without requiring additional contrast agents, which may perturb the tissue under investigation. In addition, no electric potential needs to be applied, and the measurements are not affected by electromagnetic fields. Currently, promising approaches include Raman fiber techniques and nonlinear Raman spectroscopy. Infrared spectroscopy is also being used to examine freshly resected tissue ex vivo in the operating theater. The immense volume of information contained in Raman and infrared spectra requires multivariate analysis to extract relevant information to distinguish different types of tissue. The promise and limitations of vibrational spectroscopy methods as intra-operative tools are surveyed in this review.     

The Rearrangement of 2,2‐Diphenyl‐1‐[(E)‐2‐phenylethenyl]cyclopropane to 3,4,4‐Triphenylcyclopent‐1‐ene: a DFT Analysis

A computational study on the rearrangement of 2,2‐diphenyl‐1‐[(E)‐2‐phenylethenyl]cyclopropane ( 1 ) is presented, using density functional theory (DFT), (U)B3LYP with the 6‐31G* basis set (DFT1) and (U)M05‐2X with the 6‐311+G** basis set (DFT2). In agreement with a biradical character of the transition structure (TS) or intermediate, the potential‐energy hypersurface is lowered by the influence of three conjugated Ph groups. Surprisingly, two conformations of the geminal diphenyl group (different twist angles) induce two different minimum‐energy pathways for the rearrangement. Independent of the functional used, the first hypersurface harbors true biradical intermediates, whereas the second energy surface is a flat, slightly ascending slope from the starting material to the TS. The functional (U)M05‐2X with the basis set 6‐311+G** provides realistic energies which seem to be close to experiment. The activation energy for racemization of enantiomers of 1 is lower than that of rearrangement by 2.5 kcal mol^?1, in agreement with experiment.     

Raman spectroscopic analysis of real samples: Brazilian bauxite mineralogy

In this investigation, Raman spectroscopy with 1064 and 632.8 nm excitation was used to investigate real mineral samples of bauxite ore from mines of Northern Brazil, together with Raman mapping and X-rays diffraction. The obtained results show clearly that the use of microRaman spectroscopy is a powerful tool for the identification of all the minerals usually found in bauxites: gibbsite, kaolinite, goethite, hematite, anatase and quartz. Bulk samples can also be analysed, and FT-Raman is more adequate due to better signal-to-noise ratio and representativity, although not efficient for kaolinite. The identification of fingerprinting vibrations for all the minerals allows the acquisition of Raman-based chemical maps, potentially powerful tools for process mineralogy applied to bauxite ores.     

Tetramethylcyclopentadienyl-supported rare-earth metal bis(tetramethyl)aluminate complexes: Synthesis,structural chemistry,cation formation,and isoprene polymerization

The protonolysis reaction of [Ln(AlMe₄)₃] with H(Cp′) (Cp′ = C₅Me₄H) gives access to half-sandwich complexes [(Cp′)Ln(AlMe₄)₂]. X-ray structure analyses of the samarium, neodymium, and lanthanum derivatives reveal a distinct [AlMe₄] coordination (one η², one bent η²) for the two smaller rare-earth metals. The lanthanum complex displays an unprecedented dimeric structure with two μ₂-η¹:η² coordinating [AlMe₄] ligands in the solid state. Treatment of complexes [(Cp′)Ln(AlMe₄)₂] with perfluorinated organoborates and -boranes produces discrete contact ion-pairs, which are characterized by ¹H, ¹³C, ²⁷Al, ¹⁹F, and ¹¹B NMR spectroscopy and act as efficient initiators for the fabrication of trans-1,4 polyisoprene. The polymerization performance is hereby affected by the rare-earth metal cation size, the type of boron cocatalyst, and the polymerization temperature.