Untersuchungen an Selen-Verbindungen. LVII. Über Donator-Akzeptor-Komplexe von Selensäurederivaten

The Se(VI) molecules SeO₂F₂, FeSO₂(OAlkyl), SeO₂(OCH₃)₂ and SeO₂[OSi(CH₃)₃]₂ form 1: 1 complexes with the donor molecules α,α′-dipyridyl, pyridine, trialkylamine and dioxane. The main properties, especially the thermally induced rearrangement reactions of the ester complexes, are described.     

Tetraazadibora[3, 3]paracyclophane

Starting from the para‐phenylenediamine derivative HN(SiMe₃)‐C₆H₄‐NH(SiMe₃), a lithiation and subsequent borylation give [(MeO)₂B]N(SiMe₃)‐C₆H₄‐N(SiMe₃)[B(OMe)₂] ( 1 ), the hydridation of which yields Li₂[(H₃B)N(SiMe₃)‐C₆H₄‐N(SiMe₃)(BH₃)] ( 2 ). Applying ZrCl₄ upon 2 initiates a condensation to give the title compound [‐N(SiMe₃)‐p‐C₆H₄‐N(SiMe₃)‐BH‐]₂, a hetero[3, 3]paracyclophane with two N‐B‐N chains that connect the para‐phenylene units. The product 3 crystallizes in the orthorhombic space group P2₁2₁2₁.     

1‐Oxa‐nido‐dodecaborate [OB11H12]− from the Controlled Oxidation of the closo‐Borates [B11H11]2− and [B12H12]2−

The closo‐dodecaborate [B₁₂H₁₂]^2? is degraded at room temperature by oxygen in an acidic aqueous solution in the course of several weeks to give B(OH)₃. The degradation is induced by Ag²⁺ ions, generated from Ag⁺ by the action of H₂S₂O₈. Oxa‐nido‐dodecaborate(1?) is an intermediate anion, that can be separated from the reaction mixture as [NBzlEt₃][OB₁₁H₁₂] after five days in a yield of 18 %. The action of FeCl₃ on the closo‐undecaborate [B₁₁H₁₁]^2? in an aqueous solution gives either [B₂₂H₂₂]^2? (by fusion) or nido‐B₁₁H₁₃(OH)^? (by protonation and hydration), depending on the concentration of FeCl₃. In acetonitrile, however, [B₁₁H₁₁]^2? is transformed into [OB₁₁H₁₂]^? by Fe³⁺ and oxygen. The radical anions [B₁₂H₁₂] ^{˙ ?} and [B₁₁H₁₁] ^{˙ ?} are assumed to be the primary products of the oxidation with the one‐electron oxidants Ag²⁺ and Fe³⁺, respectively. These radical anions are subsequently transformed into [OB₁₁H₁₂]^? by oxygen. The crystal structure analysis shows that the structure of [OB₁₁H₁₂]^? is derived from the hypothetical closo‐oxaborane OB₁₂H₁₂ by removal of the B3 vertex, leaving a non‐planar pentagonal aperture with a three‐coordinate O vertex, as predicted by NMR spectra and theory.     

New photochromic 2H-1.4-oxazines and spiro-2H-1.4-oxazines

The synthesis and the photochemical behaviour of 4 new 2H-1.4-oxazines and 3 new spiro-2H-1.4-oxazines is described.     

The reaction of decaborane with hydrazoic acid: A novel access to azaboranes

The reaction of B₁₀H₁₂(SMe₂)₂ ( 1 ) with HN₃ yields arachno-B₁₀H₁₂(N₃)(NH₂) ( 2 ), a product with a μ-NH₂ group. Compound 2 can be hydrolysed to give the known arachno-B₉H₁₃(NH₃) ( 3 ). nido-NB₉H₁₁(N₃) ( 4 ) is formed from 2 by a deprotonation/protonation sequence. The azaborane nido-NB₁₀H₁₃ ( 5 ) is a product of the thermolysis of 2 . The structures of 2–5 are elucidated by 2-D COSY ¹¹B–¹¹B NMR spectra; the structure of 2 is also elucidated by an X-ray structure analysis.     

Temperature dependence of ferromagnetic resonance in permalloy/NiO exchange-biased films

The temperature dependencies of the ferromagnetic resonance (FMR) linewidth and the resonance field-shift have been investigated for NiO/NiFe exchange-biased bilayers from 78 K to 450 K. A broad maximum in the linewidth of 500 Oe, solely due to the exchange-bias, is observed at ≈150 K when the magnetic field is applied along the film plane. When the magnetic field is applied perpendicular to the film plane, the maximum in the linewidth is less pronounced and amounts to 100 Oe at the same temperature. Such a behavior of the FMR linewidth is accompanied with a monotonic increase in the negative resonance field-shift with decreasing temperature. Our results are compared with the previous experimental FMR and Brillouin light scattering data for various ferromagnetic/antiferromagnetic (FM/AF) structures, and suggest that spin dynamics (spin-wave damping and anomalous resonance field-shift) in the FM/AF structures can be described in a consistent way by a single mechanism of the so-called slow-relaxation.