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.     

Experimental Study of Small-Scale Spatial Variation in Filtration Coefficient Using Tracer Method

The procedure for studying the nonuniformity of filtration flows in capillary-porous media was developed. Time dependences of local filtration coefficients averaged over the area and their spatial variation during the flow of water and aqueous electrolyte solutions were studied on soil samples of undisturbed structure using tracer method. It was found that the transformation of a pore space structure accompanied with reverse variations in pore sizes occurs because of the action of disjoining pressure in thin films depending on the ion nature. Relaxation times corresponding to the times necessary to attain equilibrium within interlayer gaps of clay minerals were determined. The conclusion was made that if the system volume is constant, the variations in the pore space structure take place because of decrease in the relative fraction of macropores and their sizes.     

Exchange and magnetic dipole-dipole interactions in bi- and triradical complexes of Al(III), Ga(III), In(III), and Sn(IV) witho-semiquinones. PM3 calculation

Semiempirical (PM3 with CI) calculations of exchange interactions for the triradical complexes of Al(III), Ga(III), and In(III) and the biradical complex of Sn (IV) with o-semiquinones are carried out. The results are in agreement with both qualitative theoretical assumptions and experimental data. The calculations indicate that the superexchange via the unoccupied porbitals of the central metal ion predominantly determines the multiplicity of the ground states of the complexes. Zero-field splitting constants D are calculated; they also agree well with experimental data. Deceased. Translated fromZhumal Struktumoi Khimii, Vol. 38, No. 6, pp. 1053–1060, November–December, 1997.