NMR and X‐ray crystallographic studies of linear and cyclic aminomethanephosphinates

We report the preparation of four diastereoisomeric pairs of ethyl {[(3‐hydroxypropyl)‐ amino](aryl)methyl}phenylphosphinates. In two cases, the phosphinates were transformed to 1,4,2‐oxazaphosphepane heterocycles through one‐pot intramolecular esterification. The analogous reaction with formaldehyde gave the six‐membered ethyl (1,3‐oxazinan‐3‐ylmethyl)phenylphosphinate, which could be transformed in a posterior reaction to the corresponding aminomethanephosphinic acid. The new compounds were characterized by IR, ¹H, ¹³C, and ³¹P NMR. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:81–87, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20179     

SPSA vs Simplex in statistical machine translation optimization

Most statistical machine translation systems are combinations of various models and tuning scaling factors is an important step. However, this optimisation problem is hard because the objective function has many local minima and the available algorithms cannot achieve a global optimum. Consequently, optimisations starting from different initial settings can converge to fairly different solutions. We present tuning experiments with the Simultaneous Perturbation Stochastic Approximation (SPSA) algorithm, and compare them with the widely used downhill simplex method. With IWSLT 2005 Chinese-English data, both methods showed similar performance, but SPSA was more robust to the choice of initial settings. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thermodynamic equilibrium between locally excited and charge-transfer states through thermally activated charge transfer in 1-(pyren-2′-yl)-o-carborane

Reversible conversion between excited-states plays an important role in many photophysical phenomena. Using 1-(pyren-2′-yl)-o-carborane as a model, we studied the photoinduced reversible charge-transfer (CT) process and the thermodynamic equilibrium between the locally-excited (LE) state and CT state, by combining steady state, time-resolved, and temperature-dependent fluorescence spectroscopy, fs- and ns-transient absorption, and DFT and LR-TDDFT calculations. Our results show that the energy gaps and energy barriers between the LE, CT, and a non-emissive ‘mixed’ state of 1-(pyren-2′-yl)-o-carborane are very small, and all three excited states are accessible at room temperature. The internal-conversion and reverse internal-conversion between LE and CT states are significantly faster than the radiative decay, and the two states have the same lifetimes and are in thermodynamic equilibrium.

Reversible conversion between excited-states is key to many photophysical phenomena. We studied the equilibrium between LE and CT states by time-resolved and temperature-dependent fluorescence, fs- and ns-transient absorption, and LR-TDDFT calculations.     

Stereoselectivity in nucleophilic addition to unsaturated ligands bound to molybdenum : Allylic alkylation of cyclohexanone

The stereochemistry and regiochemistry of nucleophilic addition to olefinic, allylic, or diene moieties can be controlled in reactions of molybdenum complexes. The synthesis of a wide range of -allylic cyclohexanones is feasible using (η⁵-cyclopentadienyl)Mo(CO)(NO)(allyl) cations. The stereoselective preparation of (RS,SR)-2-(1-methyl-2-butenyl)cyclohexanone from the reaction of 1-pyrrolidino-1-cyclohexene with [CpMo(CO)(NO)(η³-1,3-dimethylallyl)]BF₄ illustrates the methodology.     

Inclusion of the Full Electromagnetic Interaction in Correlations and Physical Quantities

Density-density correlations in a homogeneous, isotropic, classical plasma are calculated with inclusion of the full electromagnetic interaction. This leads to isotropic homogeneous field limits, contrary to the electrostatic approximation, that is consequently not valid for small wavenumbers. Application of the theory of generalized functions, combined with Kramer Kronig relations makes it possible to deal with the integrals that occur in the transverse part, provided a nonrelativistic approximation has been applied. As a side result Kubo's formula, applied to the electric conductivity, and generally derived under restriction to the electrostatic approximation, reappears for the case that the full electromagnetic interaction is included.     

Zum Nachweis der Phenole

Ohne Zusammenfassung     

Uses of the transit time distribution in kinetic flow systems

We investigate the distribution of transit or residence times of a trace reactant in laminar flow. We present measurements of this distribution for hydrogen atoms in a typical flow system, and show that the results are consistent with known theory and previous measurements of the diffusion coefficient. The use of the measured distribution as a diagnostic of flow behavior is discussed. It is also shown that the measured or calculated transit time distribution can provide a convenient means of correcting results of kinetic measurements for the departure from plug flow. In the case of firstorder, and also second-order decay of a single reactant, this correction is a useful approximation to the more rigorous solution of the partial differential equation for diffusion and reaction in laminar flow. Effects of the deviation from plug flow on a complex rection system are illustrated qualitatively for the H + NO₂ titration system.