The role of electronic factors in reagents in controlling thestereochemistry of arylsulfenyl chlorides addition

For a series of substituted arylsulfenyl chlorides the stereochemistry of Ad_E-reactions with a series of substituted Z- and E-β-deuterostyrenes has been elucidated. Non-stereospecific reaction was observed only for the pair 2,4-dinitrobenzenesulfenyl chloride-p-methoxystyrene; for all the other reactants the reaction proceeded in a strictly stereospecific manner.     

Classification of heavy-metal fluorides. fluorides with fluorite-like cation arrangement

The main feature of fluorite structure type is four families of crystallographic planes with dense trigon cation nets which are mutually oriented as the faces of a regular octahedron. A complicated cation composition may cause lowering of general symmetry to tetragonal (only one four-fold axis remains in the octahedral complex), rhombohedral (one three-fold axis), orthorhombic, and monoclinic. The geometric parameters of the cation sublattice remain constant. They are close to the parameters of the ideal face-centered cubic cation sublattice of fluorite (the measure of similarity is 1.00–0.81). This is true for all analyzed fluoride structures and some U⁴⁺, Th⁴⁺, Zr, and Ln oxyfluorides. Thus, the concept is confirmed that the crystalline state is determined by systems of parallel planes filled by dense heavy-atom nets. Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Institute of Crystallography, Russian Academy of Sciences. Translated fromZhurnal Struktumoi Khimii, Vol. 35, No. 1, pp. 71–80, January–February, 1994. Translated by T. Yudanova     

Na*(3p)-Formation under grazing scattering of Na+-ions at an Al(111) surface

Excited Na*(3p)-atoms are observed in grazing surface-collision experiments with Na⁺-beams. Such atoms can be formed beyond a certain threshold velocity via resonant electron transfer between atomic and metallic conduction band levels due to motion of the atom relative to the surface of the metal (“kinematic resonance”). This mechanism is studied here theoretically employing two different techniques: the nonperturbative “Coupled Angular Mode” (CAM) method and the approximate “Transfer Hamiltonian” (TH) method. The calculated Na*(3p)-populations agree well with recent experimental results. Moreover, the complete density matrix of the Na*(3p)-subspace has been computed with the TH-method for ion-energies between 10 and 300 keV.     

Sulfenyl halides in the synthesis of heterocycles. 3. Interaction of perfluoro-1-ethyl-2-methyl-1-propenyl-iminochloromethanesulfenyl chloride with 1-allyl-2-methoxybenzene

Reaction of perfluoro-1-ethyl-2-methyl-1-propenyliminochloromethanesulfenyl chloride with 1-allyl-2-methoxybenzene in methylene chloride and nitromethane gives as the main products β-and β-chloro sulfides plus derivative of 2,3-dihydrobenzofuran. The reaction in nitromethane in the presence of lithium perchlorate gave a product of addition of sulfur-containing electrophiles to the double bond-a derivative of 1,3-thiazolidin-2-one-in preference to the cycloaddition product. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, 1558–1564, October, 2006.