Copper(II) complexes bearing cyclobutanecarboxylate and pyridine ligands: a new series of dinuclear paddle-wheel complexes

Monatshefte für Chemie - Chemical Monthly - Four members of a new series of paddle-wheel copper(II) complexes bearing cyclobutanecarboxylate as bridging ligand with pyridine derived ligands in...     

Of Dogs and Fleas: The Dynamics of N Uncoupled Two-State Systems

The historical Ehrenfest model dating back to 1907 describes the process of equilibration together with fluctuations around the thermal equilibrium. This approach represents a special case in the dynamics of N uncoupled two-state systems. In this article we present a generalization of the original model by introducing an additional parameter p which denotes the probability of a single state change. Analytical solutions for the probability distribution of the system's state as well as the fluctuation distribution are derived. Interestingly, close inspection of the fluctuation distribution reveals an intrinsic time scale. Sampling the system's state at much slower rates yields the familiar macroscopic exponential distribution for equilibrium processes. For faster measurements a power law extends roughly over log₁₀ N orders of magnitude followed by an exponential tail. At some point, further increases of the sampling rate merely result in a shift of the fluctuation distribution towards higher values leaving plateau at small fluctuation sizes behind. Since the generic solution is rather unwieldy, we derive and discuss simple and intuitive analytical solutions in the limit of small p and large N. Furthermore, we relax the quantization of time by considering a complementary approach in continuous time. Finally we demonstrate that the fluctuation distributions resulting from the two different approaches bear identical characteristic features.     

Asymmetric Synthesis of 3-Hydroxyprolines by Photocyclization of N-(2-Benzoylethyl)glycinamides

The chiral N-(2-benzoylethyl)-N-tosylglycinamides 1a-c were prepared from the C₂-symmetric pyrrolidines 5a-c . Irradiation of these ketones 1a-c gave cis-3-hydroxyprolinamides 10-12 in moderate to good yields (Scheme 3). The de of the photocyclizations depended on the size of the substituents in positions C(2) and C(5) of the chiral pyrrolidine auxiliaries. In addition, the de varied with the reaction temperature, allowing the determination of activation-parameter differences. The structure of products 10-12 were established by NMR and X-ray analyses.     

An FTIR study of the surface chemistry of the dynamic Si(100) surface during etching in alkaline solution

In situ FTIR spectroscopy has been used in the attenuated total reflectance (ATR) mode to investigate the surface chemistry of etching Si(100) surfaces in aqueous KOH. The effect of solution concentration and electrode potential on the Si-H vibrations has been explored and the experimental results compared with density functional theory calculations. In addition. the kinetics of surface passivation of n-Si(100) has been investigated using FTIR spectroscopy.