Synthese und Kristallstrukturen der Phosphanimin-Komplexe [Cu(μ-HNPEt3)]4(O3S–CF3)4 und [Pt2Me6(μ-I)2(μ-HNPMe3)]

Synthesis and Crystal Structures of the Phosphaneimine Complexes [Cu(μ-HNPEt₃)]₄(O₃S–CF₃)₄ and [Pt₂Me₆(μ-I)₂(μ-HNPMe₃)] The title compounds have been prepared by the reaction of copper(I)triflate with [NiBr(NPEt₃)]₄ in CH₂Cl₂ suspension in the presence of water, and by the reaction of [PtMe₃I]₄ with Me₃SiNPMe₃ in boiling toluene in the presence of cesium fluoride, respectively. According to the crystal structure determinations the cation of the copper complex forms tetrameric units [Cu(HNPEt₃)]₄⁴⁺ with S₄ symmetry with Cu–N bond lengths of 191.6 and 192.1 pm. In the platinum complex the platinum atoms are linked by two μ-I bridging atoms as well as by the μ-N atom of the HNPMe₃ ligand with Pt–N bond lengths of 228.1 and 229.5 pm.     

A comparative study for the calculation of the temperature dependent shapes of unsymmetric laminates based on finite element analysis and extended classical lamination theory

It is well known that the room-temperature shapes of unsymmetric laminates do not always conform to the predictions of classical lamination theory. Instead of being saddle shaped, as classical lamination theory predicts, the room-temperature shapes of unsymmetrically laminated composites are often cylindrical in nature. In addition, a second cylindrical shape can sometimes be obtained from the first by a simple snap-through action. Hyer examined the class of all square unsymmetric cross-ply laminates which can be fabricated from four layers, i.e., [0/0/0/90], [0/0/90/0], [0/90/0/90], [0/0/90/90], and developed an extended classical lamination theory to predict whether these laminates have a saddle shape or one or two cylindrical shapes. Finite element analysis (FEA) has just recently been used for the calculation of the room-temperature shapes of unsymmetric laminates because more sophisticated finite element codes are now available and the calculations can be made in an acceptable time. The hope is to get more accurate results for the shape and the stresses and forces that occur during the snap-through action. These results are needed for the development of active deformable composite structures based on unsymmetric laminates and incorporated shape memory alloy wires [1]. Results for different lay-ups are presented and compared.Published in Mekhanika Kompozitnykh Materialov, Vol. 31, No. 3, pp. 341–350, May–June, 1995.     

Regiospecificity in the synthesis of diaryl sulfones

The addition of arylsulfinic acids to 2-methyl-1,4-benzoquinone provides high yields of sulfones in a wide variety of solvents. The distribution of isomeric products obtained is strongly influenced by either (1) the acidity of aqueous solvents or (2) the water content of alcohol solvents. The distribution of isomeric products does not change in the various anhydrous, aprotic solvents examined.     

Substituent-directed oxidation: a simple preparation of γ and δ-lactones by oxidative cyclization of hydroxyalkenes.

Treatment of tertiary γ- and δ-hydroxyalkenes with chromium trioxide in acetic acid/acetic anhydride gives reasonable yields of γ- and δ-lactones by oxidative cyclization, with loss of one carbon. A mechanism is proposed involving formation of a chromate monoester, followed by intramolecular oxidative attack on the alkene.     

Formation of Crystalline CdSe Particles from a Single‐Source‐Precursor according to Ostwald's Rule

The formation of crystalline CdSe particles in the thermal degradation of Cd(SePh)₂·TMEDA (TMEDA = tetramethylethylenediamine) as a single‐source‐precursor was investigated by in‐situ powder X‐ray diffraction. It was shown that the primary grains were formed in the cubic zinc blende modification. After an increase in particle size by further annealing a phase transition to the thermodynamically favored hexagonal wurtzite type was detected. This behaviour indicates that, according to Ostwald's rule, the primary grains consist of the less stable polymorph due to the lower activation barrier of its formation. When the volume energy of the particles gets dominant over the surface energy, the metastable form is transformed and the system adopts the modification of lowest energy.     

Das Mathematische Labor an der Technischen Hochschule in Wien

Ohne Zusammenfassung     

Low-temperature formation of cubic β-PbF2: precursor-based synthesis and first-principles phase stability study

A precursor-based approach to the cubic β-phase of PbF(2) was developed and allowed the preparation of this high-temperature phase well below the temperature for transition from the orthorhombic α- to the cubic β-phase. The formation of β-PbF(2) from the molecular precursors Pb[Se(C(6)H(2)(CF(3))(3))](2) and Pb(C(6)H(2)(CF(3))(3))(2) is facilitated by the presence of several short PbF contacts in these molecules. The cubic form of PbF(2) was obtained as macroscopic crystals as well as nanoparticulate powder. Its formation at relatively low temperature suggested a theoretical re-investigation of the phase stabilities of the two polymorphs. The theoretical results from the Kohn-Sham density functional theory indicate that the energy content for the β-phase is slightly lower than the one for the α-phase, by 0.5-1.7 kJ mol(-1) depending on the density functional used (zero-point vibrational energy correction included).