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.     

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.