An Anionic Amido-Substituted Seven-Vertex Siliconoid Cluster

The silanide [Si₄{N(SiMe₃)Dipp}₃]⁻ ( 1 ) transforms into the anionic siliconoid cluster [Si₇{N(SiMe₃)Dipp}₃]⁻ ( 2 ) with four unsubstituted silicon atoms as a contact ion pair with [K([18]crown-6)] in C₆D₆ at room temperature within five weeks. Anion 2 was investigated by natural population analysis and visualization of intrinsic atomic orbitals. Magnetically induced current-density calculations of 2 revealed two distinct strong diatropic vortices that sum up in one direction and create a strongly shielded apical silicon atom in 2 .     

Algebraic domain decomposition solver for linear elasticity

We generalize the overlapping Schwarz domain decomposition method to problems of linear elasticity. The convergence rate independent of the mesh size, coarse-space size, Korn's constant and essential boundary conditions is proved here. Abstract convergence bounds developed here can be used for an analysis of the method applied to singular perturbations of other elliptic problems.     

Efficient catalysis of Nazarov cyclization using a cationic iridium complex possessing adjacent labile coordination sites

The dicationic Ir(III) complex [IrMe(CO)(dppe)(DIB)](BARF)2 having adjacent labile sites has been found to be a very effective catalyst for promoting the Nazarov cyclization of aryl vinyl and divinyl ketones. Spectroscopic evidence for a substate-catalyst complex before cyclization is presented. The efficiency of the cyclization is attributed to the electrophilicity of the Ir(III) complex and substrate activation via chelation.     

Electron capture rates on nuclei and implications for stellar core collapse

Supernova simulations to date have assumed that during core collapse electron captures occur dominantly on free protons, while captures on heavy nuclei are Pauli blocked and are ignored. We have calculated rates for electron capture on nuclei with mass numbers A=65-112 for the temperatures and densities appropriate for core collapse. We find that these rates are large enough so that, in contrast to previous assumptions, electron capture on nuclei dominates over capture on free protons. This leads to significant changes in core collapse simulations.     

Comparison of linseed (Linum usitatissimum L.) genotypes with respect to the content of polyunsaturated fatty acids

The aim of our work was to characterize linseed (Linum usitatissimum L.) genotypes divided into groups with high and low content of alpha-linolenic acid (ALA). Out of 32 linseed genotypes, 68.75 % represented high alpha-linolenic genotypes and 31.25 % were genotypes with low ALA content. Proportional representation of fatty acids was realized according to the norm (Czech Office for Standards, Metrology and Testing, 1994). Oil content was analyzed according to the internal methodology of Agritec Ltd., based on the norm (Czech Office for Standards, Metrology and Testing, 2011). The content of total fat ranged from 36.22 % to 46.35 %, that of ALA from 1.10 % to 65.20 %, and that of linoleic acid (LA) from 11.10 % to 75.00 % in the analyzed seed samples within all groups. The genotypes were divided also according to the seed color and a linear correlation between all three parameters within these groups was observed. Negative linear dependence was confirmed between parameters; ALA and LA content in the groups: high ALA brown seed (p < 0.0001; correlation coefficient (r) = ?0.70), and high ALA yellow seed (p < 0.001; r = ?0.36). Also, positive linear dependence between the total fat and the LA content in the groups: low ALA brown seed (p < 0.001; r = 0.34); low ALA yellow seed (p < 0.0001; r = 0.62), was found.     

TbFCl2: Das erste Fluoridchlorid der dreiwertigen Lanthanoide

TbFCl₂: The First Fluoride Chloride of the Trivalent Lanthanoids Single crystals of TbFCl₂ (monoclinic, C2/c; a = 890.28(5), b = 581.56(3), c = 683.37(4) pm, β = 109.621(4)°; Z = 4) can be obtained by the reaction of TbCl₃ and TbF₃ under inert‐gas atmosphere in tantalum capsules (900 °C, 10 d) as colourless transparent lath‐shaped blocks. The crystal structure contains only one singular Tb³⁺ cation which is eightfold coordinated by two F⁻ (d(Tb³⁺−F⁻) = 218 pm, 2×) and six Cl⁻ anions (d(Tb³⁺−Cl⁻) = 280−287 pm) forming a distorted square antiprism. The F⁻ anions are linear surrounded by two Tb³⁺ cations while the Cl⁻ anions reside in a quasi‐planar coordination of three Tb³⁺ cations, therefore the Niggli formula for TbFCl₂ has to be . Terbium and fluorine form zigzag chains along the c axis that are not connected to each other and arrange like a hexagonal rod‐packing. These cationic chains are mantled by Cl⁻ anions which take care for the charge balance and the three‐dimensional cross‐linkage. The structural relationship of TbFCl₂ with YF₃‐type and PuBr₃‐type will also be discussed.     

Two Hexagonal Series of Lanthanoid(III) Oxide Fluoride Selenides: M6O2F8Se3 (M = La – Nd) and M2OF2Se (M = Nd,Sm, Gd – Ho)

Two hexagonal series of lanthanoid(III) oxide fluoride selenides with similar structure types can be obtained by the reaction of the components MF₃, M₂O₃, M, and Se in sealed niobium tubes at 850 °C using CsI as fluxing agent. The compounds with the lighter and larger representatives (M = La – Nd) occur with the formula M₆O₂F₈Se₃, whereas with the heavier and smaller ones (M = Nd, Sm, Gd – Ho) their composition is M₂OF₂Se. For both systems single‐crystal determinations were used in all cases. The compounds crystallize in the hexagonal crystal system (space group: P6₃/m) with lattice parameters of a = 1394–1331 pm and c = 403–372 pm (Z = 2 for M₆O₂F₈Se₃ and Z = 6 for M₂OF₂Se). The (M1)³⁺ cations show different square antiprismatic coordination spheres with or without an extra capping fluoride anion. All (M2)³⁺ cations exhibit a ninefold coordination environment shaped as tricapped trigonal prism. In both structure types the Se^2– anions are sixfold coordinated as trigonal prisms of M³⁺ cations, being first condensed by edges to generate trimeric units and then via faces to form strands running along [001]. The light anions reside either in threefold triangular or in fourfold tetrahedral cationic coordination. For charge compensation, both structures have to contain a certain amount of oxide besides fluoride anions. Since F^– and O^2– can not be distinguished by X‐ray diffraction, bond‐valence calculations were used to address the problem of their adjunction to the available crystallographic sites.     

Tandem Nazarov cyclization-michael addition sequence catalyzed by an Ir(III) complex

The first examples of a tandem Nazarov cyclization/Michael addition process are described. The sequence is efficiently catalyzed by Ir[Me(CO)(dppe)(DIB)]2+ and occurs with high diastereoselectivity, creating three contiguous stereocenters. The mechanistic factors controlling the reactivity and diastereoselectivity are discussed.     

Determination of the interconversion energy barrier of 2,3-pentadienedioic acid enantiomers by HPLC. 2. On-column interconversion

In this paper, an HPLC method is used to determine the enantiomerization barrier of 2,3-pentadienedioic acid enantiomers. The racemate of 2,3-pentadienedioic acid was separated by HPLC on a chiral CHIROBIOTIC T column with a 90:10 (100:0.5:0.5 MeOH/HOAc/TEA)/H2O mobile phase. Peak areas of enantiomers prior to (A(+)0, A(-)0) and after the separation (A(+), A(-)), were used for calculation of the rate constants and the enantiomerization barrier, as determined by computer-assisted peak deconvolution of the peak clusters on the chromatograms. The kinetic equation for irreversible reactions was used to determine the apparent enantiomerization rate constants and the interconversion energy barrier. The dependence of the apparent enantiomerization barrier (deltaG1(app), deltaG-1(app)) on temperature was used to determine the apparent activation enthalpy (deltaH1(app), deltaH(-1)app) and entropy (deltaS1(app), deltaS-1(app)) for the interconversion of 2,3-pentadienedioic acid enantiomers, where the coefficients 1 and -1 designate the interconversions (+) --> (-) and (-) --> (+), respectively.     

Equilibrium calculations of viscosity and thermal conductivity across a solid-liquid interface using boundary fluctuations

We calculate viscosity and thermal conductivity in systems of Lennard-Jones particles consisting of coexisting solid and liquid with different interface wetting properties using the recently developed equilibrium boundary fluctuation theory. We compare the slip length and equivalent liquid length obtained from these calculations with those obtained from nonequilibrium molecular dynamics. The equilibrium and nonequilibrium calculations of the slip length and the sum of the thermal equivalent lengths are in good agreement. We conclude that for both interfacial properties, the nonequilibrium simulations were probing the linear response. The significant dependence of the intrinsic equivalence length on the interfacial temperature difference used to generate the thermal gradient is explained as a consequence of the different thermodynamic states of the two interfaces.