Rißbildung,Nachgiebigkeit und Bruch in Polycarbonat und Polyäthylenterephthalat bei tiefen Temperaturen

Ohne Zusammenfassung     

Nouveaux thiochlorures de molybdène(II): Mo6Cl10Y (Y = S,Se, Te): Structure et propriétés magnétiques et électriques

The thiochlorides Mo₆Cl₁₀Y (Y = S, Se, Te) have been prepared; they are isostructural with Nb₆I₁₁, space group Pccn, and have four formula units per unit cell. The X-ray structure of Mo₆Cl₁₀Se has been determined from three-dimensional single-crystal counter data and refined to a final R value of 0.053 for 3350 independent reflections. The most important result concerning this structure is a statistical distribution of the Se atom on the unit (Mo₆X′₈) with $\text{X′ ?}\text{7}\text{8}\text{Cl}\text{+}\text{1}\text{8}\text{Se}$: so the compound Mo₆Cl₁₀Se must be formulated $\text{(Mo}{}_6\text{Cl}{}_7\text{Se)Cl}{}_{\mathrm{<mtext>4</mtext><mtext>2</mtext>}}\text{Cl}{}_{\mathrm{<mtext>2</mtext><mtext>2</mtext>}}$. The diamagnetic and dielectric behavior of these new thiochlorides is discussed.     

New Catalytic Synthesis of Polyfluoroalkyl Chlorosulfites

Russian Journal of General Chemistry -     

Ionization and Tautomerism of Hydroxyxanthenes and Some Other Dyes in Ethanol

Protolytic equilibria of hydroxyxanthene dyes, Fluorescein, Eosin, as well as of some relatedcompounds, in ethanol were studied by spectrophotometry. Stepwise ionization and tautomeric equilibriumconstants were determined.     

The Claisen-Schmidt reaction with heterocyclic analogs of o-hydroxyacetphenone

Claisen-Schmidt condensation of 4-hydroxy-3-acetyl-6-methylpyrid-2-one, and its N-methyl and N-phenyl derivatives with aromatic aldehydes is investigated, and it is shown that the products of this reaction are 3-cinnamoyl and not 6-styryl derivatives.     

S=N versus S+-N-: an experimental and theoretical charge density study

To elucidate the bonding situation in the widely discussed hypervalent sulfur nitrogen species, the charge density distributions rho(r) and related properties of four representative compounds, methyl(diimido)sulfinic acid H(NtBu)(2)SMe (1), methylene-bis(triimido)sulfonic acid H(2)C[S(NtBu)(2) (NHtBu)](2) (2), sulfurdiimide S(NtBu)(2) (3), and sulfurtriimide S(NtBu)(3) (4), were determined experimentally by high-resolution low-temperature X-ray diffraction experiments (T = 100 K). This set of molecules represents an ideal frame of reference for the comparison of SN bonding modes, because they contain short formal S=N double bonds as well as long S-N single bonds, some of them influenced by inter- or intramolecular hydrogen bonds. For comparison, the gas-phase ab initio calculations of the four model compounds, H(NMe)(2)SMe, H(2)C[S(NMe)(2)(NHMe)](2), S(NMe)(2), and S(NMe)(3), were performed. The topological features were found to be not particularly sensitive with respect to different substituents R (R = H, Me, tBu). In this paper, it is documented that theory and experiment differ in the eigenvalues of the Hessian matrix because of systematically differing positions of the bond critical points but agree very well concerning the spatial Laplacian distribution and the distinct polarization of all investigated sulfur-nitrogen bonds. Both recommend the S(+)-N(-) formulation of sulfur nitrogen bonds in 1 and 2 since all nitrogen atoms are found to be sp(3) hybridized. The planar SNx (x = 2, 3) units in the diimide 3 and the triimide 4 reveal characteristics of m-center-n-electron systems. For none of the investigated S-N bonds, a classical double bond formulation can be supported. This is further substantiated by the NBO/NRT approach. Valence expansion to more than eight electrons at the sulfur atom can definitely be excluded to explain the bonding.