Solution Phase Reactivity of Dibenzo[c,e][1,2]azaborinine: Activation and Insertion into Si-E Single Bonds (E=H,OSi(CH3)3, F,Cl) by a BN-Aryne

The boron-nitrogen analogue of ortho-benzyne, 1,2-azaborinine, is a reactive intermediate that features a formal boron-nitrogen triple bond. We here show by combining experimental and computational techniques that the Lewis acidity of the boron center of dibenzo[c,e][1,2]azaborinine allows interaction with the silicon containing single bonds Si−E through the silicon bonding partner E (E=F, Cl, OR, H). The binding to boron activates the Si−E bonds for subsequent insertion reaction. This shows that the BN-aryne is a ferocious species that even can activate and insert into the very strong Si−F bond.     

Sc Solid State NMR studies of the silicides ScTSi (T=Co, Ni, Cu, Ru, Rh, Pd, Ir, Pt)

The silicides ScTSi (T=Fe, Co, Ni, Cu, Ru, Rh, Pd, Ir, Pt) were synthesized by arc-melting and characterized by X-ray powder diffraction. The structures of ScCoSi, ScRuSi, ScPdSi, and ScIrSi were refined from single crystal diffractometer data. These silicides crystallize with the TiNiSi type, space group Pnma. No systematic influences of the ⁴⁵Sc isotropic magnetic shift and nuclear electric quadrupolar coupling parameters on various structural distortion parameters calculated from the crystal structure data can be detected. ⁴⁵Sc MAS-NMR data suggest systematic trends in the local electronic structure probed by the scandium atoms: both the electric field gradients and the isotropic magnetic shifts relative to a 0.2 M aqueous Sc(NO₃)₃ solution decrease with increasing valence electron concentration and within each T group the isotropic magnetic shift decreases monotonically with increasing atomic number. The ⁴⁵Sc nuclear electric quadrupolar coupling constants are generally well reproduced by quantum mechanical electric field gradient calculations using the WIEN2k code.     

Homotopy theory of bicomplexes

We define two model structures on the category of bicomplexes concentrated in the right half plane. The first model structure has weak equivalences detected by the totalisation functor. The second model structure's weak equivalences are detected by the $E^2$-term of the spectral sequence associated to the filtration of the total complex by the horizontal degree. We then extend this result to twisted complexes.     

Clark model in the general situation

For a unitary operator U in a Hilbert space H the family of its unitary perturbations by rank one operators with fixed range is parametrized by a complex parameter γ, ?γ? = 1. Namely, all such unitary perturbations are operators U_γ:= U + (γ ? 1)( ·, b₁)_Hb, where b ∈ H, ∥b∥ = 1, b₁ = U^?1b, ?γ? = 1. For ?γ? < 1, the operators U_γ are contractions with one-dimensional defects.     

Detonation waves in trinitrotoluene

Fabry-Perot, ORVIS, and VISAR laser interferometry are used to obtain nanosecond time resolved particle velocity histories of the free surfaces of copper and tantalum discs accelerated by detonating trinitrotoluene (TNT) charges and of the interfaces between TNT detonation products and lithium fluoride crystals. TNT detonation reaction zone profiles are measured for self-sustaining detonation and piston supported overdriven (supracompressed) waves. The experimental records are compared to particle velocity histories calculated using very finely zoned meshes of the exact dimensions with the DYNA2D hydrodynamic code. The Ignition and Growth reactive flow model, which is based on the Zeldovich-von Neumann-D?ring (ZND) theory of detonation, yields excellent agreement with the experimental records for TNT using an unreacted von Neumann spike pressure of 25 GPa, a reaction rate law which releases 90% of the chemical energy within 80 ns and the remaining 10% over an additional 200 ns, and a reaction product equation of state fit to cylinder test data assuming a Chapman-Jouguet pressure of 19 GPa. The late time energy release is attributed to diffusion controlled solid carbon particle formation. Received 26 July 1997 / Accepted 29 December 1997     

Anomalous Odd–Even Effects in Columnar and Smectic Phases of Discotic Tetraphenylenes

Rather uncommon but pronounced odd–even effects in the clearing temperatures of liquid crystals are found for three new homologous series of discotic tetraphenylenes (see figure). Detailed similarities to the well‐known odd‐even effects in calmitic mesogens point towards a more general understanding of odd‐even effects in liquid crystals.

     

peri-Dimethylamino substituent effects on proton transfer at carbon in α-naphthylacetate esters: a model for mandelate racemase

The rate constants for exchange of hydrogen for deuterium at the α-CH(2) positions of 8-(N,N-dimethylaminonaphthalen-1-yl)acetic acid tert-butyl ester 1 and naphthalen-1-ylacetic acid tert-butyl ester 2 have been determined in potassium deuteroxide solutions in 1 : 1 D(2)O : CD(3)CN, in order to quantify the effect of the neighbouring peri-dimethylamino substituent on α-deprotonation. Intramolecular general base catalysis by the (weakly basic) neighbouring group was not detected. Second-order rate constants, k(DO), for the deuterium exchange reactions of esters 1 and 2 have been determined as 1.35 × 10(-4) M(-1) s(-1) and 3.95 × 10(-3) M(-1) s(-1), respectively. The unexpected 29-fold decrease in the k(DO) value upon the introduction of a peri-dimethylamino group is attributed to an unfavourable steric and/or electronic substituent effect on intermolecular deprotonation by deuteroxide ion. From the experimental k(DO) values, carbon acid pK(a) values of 26.8 and 23.1 have been calculated for esters 1 and 2.