Le probleme de la conjugaison a travers un atome de silicium π-lie dans les systemes sila-2 butadieniques

The chemical behaviour of sila-2 butadienes, formed as transient intermediates either by thermolysis or by photolysis of various 1-vinylsilacyclobutanes, was studied with respect to hydroxylated compounds of different pKa values Two mechanisms can explain the nature of the products obtained on the co-thermolysis of the cyclic compounds with phenol, one with 1-silacyclobut-1-ene intermediate and the other involving an allylic silicenium cation. In both hypothetical mechanisms, the 2-silabutadienes behave as a conjugated system since they lead either to (2+2) cycloaddition or to (1,2)- and (1,4)-electrophilic addition. This evidence for a conjugation phenomenon through a silicon atom is supported by the calculation of the delocalisation energies of butadiene and 2-silabutadiene.     

Application of strategically designed sample composition to the rapid analytical screening of milk samples for polychlorinated biphenyls

Strategically designed sample composition (SSC) is a new technique that decreases the number of analytical determinations needed in routine screening to as few as the number of original sample specimens while providing information that is specific to them. Although this new technique has been applied to environmental studies, this paper describes its first application to food safety studies. Contamination of milk samples with polychlorinated biphenyls (PCBs) was chosen as a case study to show the usefulness and potential of the SSC technique with a fast analytical procedure that involves saponification of the samples and solid-phase microextraction of the PCBs. A total of 20 sample specimens can be analyzed in 11 determinations with excellent predictions of the positive samples and the concentration levels of the contaminants. The robustness of the strategy was investigated and demonstrated.     

Conductance in homomorphous solvents: Tetrabutylammonium salts and alkali picrates in butyrolactone-sulfolane mixtures

Conductance measurements are reported for LiPi, NaPi, KPi, RbPi, CsPi, Bu₄NPi, Bu₄NBr, Bu₄NClO₄, Bu₄NNO₃, and Bu₄NBBu₄ at 25°C in -butyrolactone-sulfolane mixtures. In these mixtures of solvents that are practically homomorphous, isodielectic and with comparable dipole moments, the ion pair association and ionic mobilities of large ions conform to the expectations of the primitive model. Electrolytes containing lithium or sodium ions show anomalies indicating that other factors besides shape, dipole moment, and polarizability of the solvent molecules are involved in the association and transport processes of these ions.     

Molybdenum(VI) and molybdenum(V) mononuclear and dinuclear complexes with 1,3-diphenyl-1,3-propanedione

Summary The synthesis and the dinuclear or mononuclear nature of several molybdenum(VI) and molybdenum(V) oxocomplexes derived from 1,3-diphenyl-1,3-propanedione (HLL) are described. These complexes were identified by i.r. and electronic spectra, magnetic susceptibility and analytical data, and are assigned the following formulae: [MoO₂(LL)₂], [Mo₂O₅(LL)₂], [Mo₂O₄(LL)₂], [MoOCl(LL)₂], [MoCl₂(LL)] and [MoO(OH)(LL)₂)]. The low magnetic moments of the dinuclear complexes are due, in part, to intramolecular interactions. The i.r. data show that the dionate is bound by two oxygen atoms forming a chelate six-membered ring.     

Hemithio-analogues of meisenheimer complexes and sulphide group activation of aromatic substitution by alkoxides

EtO^? in DMSO adds to ethylthiopicrate at C-3 to generate an ephemeral

-adduct which ends into 1-ethylthio-4-ethoxy-2,5-dinitrobenzene, whilst ethyl picrate gives two adducts of attack of EtS^? at C-3 or C-1.     

About the calculation of exchange coupling constants in polynuclear transition metal complexes

The application of theoretical methods based on the density functional theory with hybrid functionals provides good estimates of the exchange coupling constants for polynuclear transition metal complexes. The accuracy is similar to that previously obtained for dinuclear compounds. We present test calculations on simple model systems based on H. He and CH(2). He units to compare with Hartree-Fock and multiconfigurational results. Calculations for complete, nonmodeled polynuclear transition metal complexes yield coupling constants in very good agreement with available experimental data.     

Determination of propazine by differential pulse polarography in micellar and emulsified media

An electroanalytical study of the herbicide propazine's reduction process in micellar solutions and oil-in-water emulsions is reported. The anionic surfactant sodium pentanesulphonate was chosen as the most suitable. The differential pulse polarograms of micellar solutions had two reduction peaks below pH 2.0, whereas only one peak was obtained above pH 2.O. Ethyl acetate was chosen as the organic solvent to form propazine emulsions. Unlike in micellar solutions, the DPP polarograms of propazine emulsions showed only one peak even at pH < 2.0, suggesting that propazine hydrolysis was hindered in the emulsified medium. The limiting current is diffusion-controlled and the electrode process is irreversible. Propazine can be determined by differential pulse polarography over the 1.0 × 10^–1 – 1.0 × 10^–1moll^–1 and 1.0 × 10^–15 – 4.0 × 10^–1 moll^–1 concentration ranges and the limit of detection was 2.8 × 10^–1 moll^–1. Of the potential interferents simazine, methoprotryne and terbutryn (alls-triazines), thiram (a dithiocarbamate), dinoseb (nitrophenolic), and heptachlor (chlorinated cyclo-diene herbicide), only the first two were significant (10% error for equimolar concentrations). The method was applied to the determination of propazine in spiked drinking water. At a concentration level of 2.0 × 10^–1 moll^–1 a recovery of 94 ± 6% was obtained, after tenfold concentration on Sep-Pak.     

On the 2 and the 3-connectedness of ample divisors on a surface

Let X be a nonsingular complex projective surface and let D be an ample divisor on X such that the associated invertible sheaf is spanned by its global sections. We prove that D is 2-connected apart from a few cases we explicitly describe. We also provide a corresponding result for the 3-connectedness when D²10 and for the 4-connectedness when D²17 and D is very ample.