The hydration of the uranyl dication: Incorporation of solvent effects in parallel density functional calculations with the program PARAGAUSS

The parallel density functional program PARA GAUSS has been extended by a tool for computing solvent effects based on the conductor‐like screening model (COSMO). The molecular cavity in the solvent is constructed as a set of overlapping spheres according to the GEPOL algorithm. The cavity tessellation scheme and the resulting set of point charges on the cavity surface comply with the point group symmetry of the solute. Symmetry is exploited to reduce the computational effort of the solvent model. To allow an automatic geometry optimization including solvent effects, care has been taken to avoid discontinuities due to the discretization (weights of tesserae, number of spheres created by GEPOL). In this context, an alternative definition for the grid points representing the tesserae is introduced. In addition to the COSMO model, short‐range solvent effects are taken into account via a force field. We apply the solvent module to all‐electron scalar‐relativistic density functional calculations on uranyl, UO₂²⁺, and its aquo complexes in aqueous solution. Solvent effects on the geometry are very small. Based on the model [UO₂(H₂O)₅]²⁺, the solvation energy of uranyl is estimated to be about ?400 kcal/mol, in agreement with the range of experimental data. The major part of the solvation energy, about ?250 kcal/mol, is due to a donor–acceptor interaction associated with a coordination shell of five water ligands. One can interpret this large solvation energy also as a compounded effect of an effective reduction of the uranyl moiety plus a solvent polarization. The energetic effect of the structure relaxation in the solution is only about 8 kcal/mol. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

Novel Aspects in the Synthesis of Carbenoids Containing P/C-pπ-Bonds

Abstract

The synthesis and x-ray structure analysis of a novel type of carbenoids, aryl-P(=E)=C(Cl)Li(thf)₃ (E=N-aryl, C(SiMe₃)₂), as well as the first example of a 1,3-diphosphetane-2,4-diyl, (aryl-PCCl)₂, is reported and on the basis of quantum chemical calculations its bonding situation is discussed. Furthermore, selected examples for the varying reaction behavior of both types of compounds are presented.     

Horizontal bridges in polar dielectric liquids

When a high-voltage direct-current is applied to two beakers filled with polar liquid dielectrica like water or methanol, a horizontal bridge forms between the two beakers. By repeating a version of Pellat’s experiment, it is shown that a horizontal bridge is stable by the action of electrohydrodynamic pressure. Thus, the static and dynamic properties of the phenomenon called a ‘floating water bridge’ can be explained by the gradient of Maxwell pressure, replenishing the liquid within the bridge against any drainage mechanism. It is also shown that a number of liquids can form stable and long horizontal bridges. The stability of such a connection, and the asymmetry in mass flow through such bridges caused by the formation of ion clouds in the vicinity of the electrodes, is also discussed by two further experiments.     

A Highly Selective Synthesis of a Chiral Gamma-amino Trisubstituted Z-Vinyl Ester.1

Application of the Clark Still trifluorethyl phosphonate varient of the Wadsworth-Emmons reaction with a chiral alpha-amino aldehyde results in the highly selective synthesis of a trisubstituted Z-vinyl ester.     

The Ene-Reaction of Phosphaalkynes-Application for the Synthesis of Phosphiranes

Abstract

1,3-Butadienes 1 and 6-Methyl-2H-pyran-2-ones 6 react with two equivalents of phosphaalkynes 2 in a domino-reaction to the diphosphiranes 5 and 9 respectively. Diels-Alder-reaction of 1 with 2 leads to 3 which cannot be isolated. An Ene-reaction of the phosphacyclohexa-1,4-diene 3 with additional 2 gives 4 followed by an intramolecular Diels-Alder-reaction yielding the stable diphosphatricyclooctenes 5.     

An Intramolecular Diels-alder Reaction of a Z-Diene. Generation Of The Chiral Isoindolone Nucleus Of Cytochalasin C.1

Aldol/elimination reactions of ß-ketoamides with methyl glyoxylate result in highly selective production of Z-α,ß-unsaturated amides. An intramolecular Diels-Alder reaction of a triply activated dienophile derived from chiral dienylamine 7ZE stereospecifically affords chiral bicyclic lactam 11 at room temperature.     

The morphology of submicronsized core-shell latex particles: an electron microscopy study

The core-shell structure of a range of acrylic-acrylic latexes has been investigated by combining different specimen preparation methods with transmission electron microscopy (TEM), dark-field scanning transmission electron microscopy (DSTEM) and low-voltage scanning electron microscopy (LV-SEM), including the first reported use of LV-SEM to observe composite latex particles at ambient and subambient temperatures. Spin-coating of liquid latex dispersions directly onto TEM grids or SEM stubs is shown to be a relatively straightforward mean of avoiding film formation during specimen preparation. In conjunction with double staining techniques, it has been found to be particularly convenient for characterizing the fine structure of particles with diameters down to below 100 nm.     

Polymorphs of the Gadolinite-Type Borates ZrB2O5 and HfB2O5 Under Extreme Pressure

Based on the results from previous high-pressure experiments on the gadolinite-type mineral datolite, CaBSiO₄(OH), the behavior of the isostructural borates β-HfB₂O₅ and β-ZrB₂O₅ have been studied by synchrotron-based in situ high-pressure single-crystal X-ray diffraction experiments. On compression to 120 GPa, both borate layer-structures are preserved. Additionally, at ≈114 GPa, the formation of a second phase can be observed in both compounds. The new high-pressure modification γ-ZrB₂O₅ features a rearrangement of the corner-sharing BO₄ tetrahedra, while still maintaining the four- and eight-membered rings. The new phase γ-HfB₂O₅ contains ten-membered rings including the rare structural motif of edge-sharing BO₄ tetrahedra with exceptionally short B−O and B⋅⋅⋅B distances. For both structures, unusually high coordination numbers are found for the transition metal cations, with ninefold coordinated Hf⁴⁺, and tenfold coordinated Zr⁴⁺, respectively. These findings remarkably show the potential of cold compression as a low-energy pathway to discover metastable structures that exhibit new coordinations and structural motifs.