Catalytic asymmetric deprotonation of a phosphine borane: comparison of two-ligand and one-ligand catalysis

The catalytic asymmetric deprotonation of tert-butyldimethylphosphine borane using s-BuLi or n-BuLi and sub-stoichiometric amounts of (?)-sparteine under one-ligand and two-ligand manifolds has been investigated. Using s-BuLi, slightly higher enantioselectivity was obtained using two-ligand catalysis (use of sub-stoichiometric (?)-sparteine in the presence of a stoichiometric amount of a second achiral ligand) compared to one-ligand catalysis (use of sub-stoichiometric (?)-sparteine only). With n-BuLi, two-ligand catalysis using LiDMAE (DMAE = dimethylaminoethanol) as the stoichiometric ligand was the only method for obtaining good yield and enantioselectivity. In this case, one-ligand catalysis failed as the (?)-sparteine was not turned over.     

Ueber Stabilität und Dispersitätsgrad

Ohne ZusammenfassungAutoreferat eines in der chemischen Sektion der naturwissensch. Studenten-Gesellschaft in Upsala im Frühjahr 1912 gehaltenen Vortrags. Die experimentellen Resultate finden sich in der Zeitschr. f. physik. Chem.78, 682–708 (1912), und bezüglich der fraktionierten Koagulation des Schwefels in der Koll.-Zeitschr.8, 186–193 (1911) wieder.     

The effect of ligand on the rate of propagation of Cu(0)‐wire catalyzed SET‐LRP of MA in DMSO at 25 °C

The effect of initial ligand concentration on the apparent rate constant of propagation of single‐electron transfer living radical polymerization (SET‐LRP) of MA in DMSO at 25 °C was examined using various lengths of Cu(0) wire as catalyst. It was determined that unlike other parameters such as initiator concentration, solvent concentration, and deactivator concentration, no simple external rate‐order for the ligand concentration could be determined. Rather, the response of the rate of SET‐LRP to initial ligand concentration is complex and is likely determined by a competition of ligand‐dependent extent of disproportionation as well as the role of ligand concentration in the surface mediated activation process. Results suggest that a minimum concentration of ligand is needed to achieve both acceptable reaction rate and reaction control, and therefore, ligand concentration must be considered in designing experimental conditions for SET‐LRP. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5629–5638, 2009     

Particle charging and charge screening in nonpolar dispersions with nonionic surfactants

The electrostatic stabilization of colloidal dispersions is usually considered the domain of polar media only because of the high energetic cost associated with introducing electric charge in nonpolar environments. Nevertheless, some surfactants referred to as "charge control agents" are known to raise the conductivity of liquids with low electric permittivity and to mediate charge stabilization of nonpolar dispersions. Here we study an example of the particularly counterintuitive charging and electrostatic interaction of colloidal particles in a nonpolar solvent caused by nonionic surfactants. PMMA particles in hexane solutions of nonionic sorbitan oleate (Span) surfactants are found to exhibit a field-dependent electrophoretic mobility. Extrapolation to zero field strength yields evidence for large electrostatic surface potentials that decay with increasing surfactant concentration in a fashion reminiscent of electrostatic screening caused by salt in aqueous solutions. The amount of surface charge and screening ions in the nonpolar bulk is further characterized via measurements of the particles' pair interaction energy. The latter is obtained by liquid structure analysis of quasi-2-dimensional equilibrium particle configurations studied with digital video microscopy. In contrast to the behavior reported for systems with ionic surfactants, we observe particle charging and a screened Coulomb type interaction both above and below the surfactant's critical micelle concentration.     

AuPt core–shell nanocatalysts with bulk Pt activity

In the presented work, the evaluation of an unsupported AuPt core–shell catalyst for the oxygen reduction reaction is introduced. Applying only basic chemicals in an upscalable synthesis route, it is demonstrated that uniform, flat, and complete Pt layers around a spherical Au core are obtained. The electrocatalytic measurements show that the surface area specific activity of the AuPt core–shell catalyst towards the important oxygen reduction reaction equals the one of polycrystalline bulk Pt. To our knowledge, this is the first time that the unfavorable particle size effect of Pt nanoparticles could be by-passed for a nanoscale catalyst.     

Towards catenanes using π-stacking interactions and their influence on the spin-state of a bis(2,2':6',2"terpyridine)iron(II) domain

The ligand 6,6"bis(4-methoxyphenyl)-4'-phenyl-2,2':6',2"terpyridine (2) has been prepared and characterized; deprotection using pyridinium chloride leads to the formation of 6,6"bis(4-hydroxyphenyl)-4'-phenyl-2,2':6',2"terpyridinium chloride ([H3]Cl). Treatment of the latter with 3-(2-(2-bromoethoxy)ethoxy)prop-1-ene under basic conditions yields ligand 4 containing pendant, alkene-terminated chains. Whereas direct complexation of 4 with ruthenium(II) proved problematical, the homoleptic complexes [Fe(2)(2)][PF(6)](2) and [Ru(2)(2)][PF(6)](2) were prepared in good to moderate yields. In the solid state, both complexes exhibit multiple face-to-face π-stacking of arene and pyridine rings which influences the coordination geometry about the metal ion. Consequential weakening of the ligand field results in [Fe(2)(2)][PF(6)](2) being high-spin. Variable temperature solution (1)H NMR spectroscopic studies confirm the iron(ii) centre remains high-spin between 200 and 295 K. The paramagnetically shifted (1)H NMR spectrum exhibits signals in the range δ 109.7 to -66.5 ppm and has been fully assigned. Paramagnetic relaxation enhancement (PRE) has been used to correlate the observed proton line-widths to the distances of the protons from the metal centre and these are in good agreement with the Fe···H separations observed in the solid state. The [Fe(2)(2)](2+) ion undergoes two dynamic processes (i) rotation of the pendant phenyl rings which is fast on the NMR timescale at 200 K, and (ii) twisting and sliding of the aromatic rings of the tpy and anisyl units which interconverts the two enantiomers of [Fe(2)(2)](2+) at 295 K.     

Simultaneous analysis of 70 pesticides using HPlc/MS/MS: a comparison of the multiresidue method of Klein and Alder and the QuEChERS method

Since 2003, two new multipesticide residue methods for screening crops for a large number of pesticides, developed by Klein and Alder and Anastassiades et al. (Quick, Easy, Cheap, Effective, Rugged, and Safe; QuEChERS), have been published. Our intention was to compare these two important methods on the basis of their extraction efficiency, reproducibility, ruggedness, ease of use, and speed. In total, 70 pesticides belonging to numerous different substance classes were analyzed at two concentration levels by applying both methods, using five different representative matrixes. In the case of the QuEChERS method, the results of the three sample preparation steps (crude extract, extract after SPE, and extract after SPE and acidification) were compared with each other and with the results obtained with the Klein and Alder method. The extraction efficiencies of the QuEChERS method were far higher, and the sample preparation was much quicker when the last two steps were omitted. In most cases, the extraction efficiencies after the first step were approximately 100%. With extraction efficiencies of mostly less than 70%, the Klein and Alder method did not compare favorably. Some analytes caused problems during evaluation, mostly due to matrix influences.