N-heterocyclic carbene-catalyzed generation of homoenolates: gamma-butyrolactones by direct annulations of enals and aldehydes

N-Heterocyclic carbenes, prepared in situ from diarylimidazolium salts, serve as highly effective catalysts for the generation of reactive homoenolates from alpha,beta-unsaturated aldehydes. The catalyst-bound homoenolate reacts with electrophilic aldehydes leading, via the key intermediacy of an activated carboxylate, to gamma-butyrolactones in good yields and stereoselectivities. Importantly, this process demonstrates an unprecedented reaction mode for the generation of nucleophilic carbanions with a multifunctional organocatalyst under exceptionally mild and convenient reaction conditions.     

Conformal properties of nonpeeling vacuum space-times

In a previous paper we investigated a class ofnonpeeling asymptotic vacuum solutions which were shown to admit finite expressions for the Winicour-Tamburino energy-momentum and angular momentum integrals. These solutions have the property that $$\psi _0 = O(r^{ - 3 - \in _0 } ), \in _0 \leqslant 2$$ and $$\psi _1 = O(r^{ - 3 - \in _1 } ), \in _1< \in _0 and \in _1< 1$$ withψ ₂,ψ ₃, andψ ₄ having the same asymptotic behavior as they do for peeling solutions. The above investigation was carried out in the physical space-time. In this paper we examine the conformal properties of these solutions, as well as the more general Couch-Torrence solutions, which include them as a subclass. For the Couch-Torrence solutions $$\begin{gathered} \psi _0 = O(r^{ - 2 - \in _0 } ) \hfill \\ \psi _1 = O(r^{ - 2 - \in _1 } ), \in _1< \in _0 {\text{ }}and \in _1 \leqslant 2 \hfill \\ \end{gathered} $$ and , $$\psi _2 = O(r^{ - 2 - \in _2 } ),{\text{ }} \in _2< \in _1 {\text{ }}and \in _2 \leqslant 1$$ withψ ₃ andψ ₄ behaving as they do for peeling solutions. It is our purpose to determine how much of the structure generally associated with peeling space-times is preserved by the nonpeeling solutions. We find that, in general, a three-dimensional null boundary (?⁺) can be defined and that the BMS group remains the asymptotic symmetry group. For the general Couch-Torrence solutions several physically and/or geometrically interesting quantities     

Einflu\ der Temperatur auf die Koagulation des kolloiden Goldes

Colloid and Polymer Science -     

Total domination dot-stable graphs

A set S of vertices in a graph G is a total dominating set if every vertex of G is adjacent to some vertex in S. The minimum cardinality of a total dominating set of G is the total domination number of G. Two vertices of G are said to be dotted (identified) if they are combined to form one vertex whose open neighborhood is the union of their neighborhoods minus themselves. We note that dotting any pair of vertices cannot increase the total domination number. Further we show it can decrease the total domination number by at most 2. A graph is total domination dot-stable if dotting any pair of adjacent vertices leaves the total domination number unchanged. We characterize the total domination dot-stable graphs and give a sharp upper bound on their total domination number. We also characterize the graphs attaining this bound.     

Deuterium kinetic isotope effects in gas-phase S(N)2 and E2 reactions: comparison of experiment and theory

The competition between bimolecular nucleophilc substitution and base-induced elimination is investigated through kinetic isotope effect measurements for gas-phase reactions of RCl + ClO- (R = methyl, ethyl, isopropyl, and tert-butyl) utilizing a FA-SIFT instrument. The overall reaction rate constants and the kinetic isotope effect for the reaction of C2H5Cl + ClO- are compared to computational results. [Hu, W. P.; Truhlar, D. G. J. Am. Chem. Soc. 1996, 118, 860.] Experimental results show that as the degree of substitution in the neutral reactant increases the E2 channel becomes dominant. The systematic change in the overall kinetic isotope effects indicates that, for the reaction of ClO- with C2H5Cl, both the SN2 and E2 pathways do occur, as predicted by computation; however the experimental reaction rate constants and KIE deviate strongly from the computational result.     

Experimental thermochemical study of two polymethylpyrazine N,N′-dioxide derivatives

The standard (p° = 0.1 MPa) molar enthalpies of formation of crystalline 2,3,5-trimethylpyrazine-1,4-dioxide and 2,3,5,6-tetramethylpyrazine-1,4-dioxide were measured, at T = 298.15 K, by static bomb calorimetry and the standard molar enthalpies of sublimation, at T = 298.15 K, were obtained from Calvet microcalorimetric measurements. These values were used to derive the respective standard molar enthalpies of formation in gaseous phase. The mean N–O bond dissociation enthalpy has been calculated for both compounds.     

A Self‐Binding,Melt‐Castable,Crystalline Organic Electrolyte for Sodium Ion Conduction

The preparation and characterization of the cocrystalline solid–organic sodium ion electrolyte NaClO₄(DMF)₃ (DMF=dimethylformamide) is described. The crystal structure of NaClO₄(DMF)₃ reveals parallel channels of Na⁺ and ClO₄^? ions. Pressed pellets of microcrystalline NaClO₄(DMF)₃ exhibit a conductivity of 3×10^?4 S cm^?1 at room temperature with a low activation barrier to conduction of 25 kJ mol^?1. SEM revealed thin liquid interfacial contacts between crystalline grains, which promote conductivity. The material melts gradually between 55–65 °C, but does not decompose, and upon cooling, it resolidifies as solid NaClO₄(DMF)₃, permitting melt casting of the electrolyte into thin films and the fabrication of cells in the liquid state and ensuring penetration of the electrolyte between the electrode active particles.     

The influence of core geometry on the crystallography of silicon optical fiber

Crystalline semiconductor core optical fibers have received growing attention as greater understanding of the underlying materials science, coupled with advances in fiber processing and fabrication, have expanded the quality and portfolio of available materials. In a continued effort to better understand the nature of the crystal formation this work studies the role of the cross-sectional geometry on the resultant core crystallography with respect to the fiber axis. More specifically, a molten-core approach was used to fabricate silicon optical fibers clad in silica tubes of either circular or square inner cross-sections. In both geometric cases, the silicon core was found to possess regions of single crystallinity where specific crystal orientations persisted along a fiber length of about 4–5 mm prior to transitioning through polycrystalline regions. However, the rotation and tilting angular combination needed to align a given crystallographic axis with the fiber axis was more constant over the single crystalline region in the case of the square-core fiber while more significant variations were observed in the round-core case. This work begins to elucidate some of the microstructural features, not present in conventional glass optical fibers, that could be important for future low-loss single crystalline semiconductor optical fibers.     

Synthesis and crystal structures of some bis(3‐methyl‐1H‐indol‐2‐yl)(salicyl)methanes

Four 2,2′‐bisindolylmethanes (BIMs), a useful class of polyindolyl species joined to a central carbon, were synthesized using salicylaldehyde derivatives and simple acid catalysis; these are 2‐[bis(3‐methyl‐1H‐indol‐2‐yl)methyl]‐6‐methylphenol, (IIa), 2‐[bis(3‐methyl‐1H‐indol‐2‐yl)methyl]‐4,6‐dichlorophenol, (IIb), 2‐[bis(3‐methyl‐1H‐indol‐2‐yl)methyl]‐4‐nitrophenol, (IIc), and 2‐[bis(3‐methyl‐1H‐indol‐2‐yl)methyl]‐4,6‐di‐tert‐butylphenol, (IId). BIMs (IIa) and (IIb) were characterized crystallographically as the dimethyl sulfoxide (DMSO) disolvates, i.e. C₂₆H₂₄N₂O·2C₂H₆OS and C₂₅H₂₀Cl₂N₂O·2C₂H₆OS, respectively. Both form strikingly similar one‐dimensional hydrogen‐bonding chain motifs with the DMSO solvent molecules. BIM (IIa) packs into double layers of chains whose orientations alternate every double layer, while (IIb) forms more simply packed chains along the a axis. BIM (IIa) has a remarkably long c axis.     

Structurally Diverse Boron–Nitrogen Heterocycles from an N2O23− Formazanate Ligand

Five new compounds comprised of unprecedented boron–nitrogen heterocycles have been isolated from a single reaction of a potentially tetradentate N₂O₂³⁻ formazanate ligand with BF₃⋅OEt₂ and NEt₃. Optimized yields for each product were obtained through variation of experimental conditions and rationalized in terms of relative Gibbs free energies of the products as determined by electronic structure calculations. Chemical reduction of two of these compounds resulted in the formation of a stable anion, radical anion, and diradical dianion. Structural and electronic properties of this new family of redox-active heterocycles were characterized using UV/vis absorption spectroscopy, cyclic voltammetry and X-ray crystallography.