About the Keggin isomers: crystal structure of [N(C4H9)4]-gamma-[SiMo2W10O40]n- (n= 4 or 6)

The tetrabutylammonium gamma-dodecatungstosilicate has been crystallized in a 6/1 acetonitrile/water solvent. An X-ray single-crystal analysis was carried out on [N(C4H9)4]4-gamma-[SiW12O40] which crystallizes in the orthorhombic system, space group P2(1)2(1)2(1), with a = 19.0881(3) A, b = 21.4435(3) A, c = 26.0799(1) A, V = 10674.9(2) A3, Z = 4, and rho(calcd) = 2.392 g/cm3. The idealized C2v arrangement of the anion results from the rotation of 60 degrees of two trigonal [W3O13] groups in the Keggin anion. Taking as reference the geometrical characteristics of the Keggin anion, it appears that the bond lengths and bonds angles within the four [W3O13] groups are not significantly modified while the mu-oxo junctions between the two rotated groups and those between the two unrotated groups involve more acute and opened W-O-W angles, respectively. The syntheses and 183W NMR characterizations of the mixed gamma-[SiW10Mo2O40]n- compounds corresponding to the oxidized (Mo(VI); n = 4) and to the two electron-reduced (Mo(V); n = 6) anions are reported. Structural analysis by 183W NMR has proved unambiguously that the C2v structure of the gamma-[SiW10O36]8- subunit is retained in both the compounds. The electronic behavior of the series gamma-[SiW10M2E2O36]6- (M = Mo or W; E = O or S) is examined, compared and related to 183W NMR data.     

Efficient and fast Heck vinylation of 2-bromo-6-methyl pyridines with methylacrylate. Application to the synthesis of 6-methyl cyclopenta[b]pyridinone

Heck vinylation of 2-bromo-6-methyl-3-substituted pyridines using η³-allylpalladium chloride dimer/P(o-Tol)₃ complex/toluene and dimethylacetamide (DMA) as co-solvent with methyl acrylate is reported. Electronic and steric effects were investigated engaging diversely 2-bromo-3,6-disubstituted pyridines. As application, a new synthesis of the 6-methyl cyclopenta[b]pyridinone building-block connecting Heck vinylation, alkene reduction and Dieckmann condensation is described.     

A parachute for the degree of a polynomial in algebraically independent ones

We give a simpler proof as well as a generalization of the main result of an article of Shestakov and Umirbaev. This latter article being the first of two that solve a long-standing conjecture about the non-tameness, or “wildness”, of Nagata’s automorphism. As corollaries we get interesting informations about the leading terms of polynomials forming an automorphism of K[x ₁, . . . , x _n ] and reprove the tameness of automorphisms of K[x ₁, x ₂].     

Effets du solvant et du complexant sur le contrŏlw xinétique et thermodynamique de la métallation. Cas de la diméthyl-4,4 (thiényl-2)-w oxzaoline

The metallation of the title compound bu n-butyllithium is largely dependent on solvent, temperature, and starting material concentration. Under ki     

Bis(diethoxyselenophosphinoyl) triselenide and bis(diisopropoxyselenophosphinoyl) diselenide

The title compounds, bis(diethoxyselenophosphinoyl) triselenide, [P(OEt)₂Se]Se₃[P(OEt)₂Se], and bis­(diisopropoxy­selenophosphinoyl) diselenide, [P(OⁱPr)₂Se]Se₂[P(OⁱPr)₂Se], comprise an Se₃ chain or an Se₂ chain bridging two (RO)₂PSe groups.     

Chiral Anthranyl Trifluoromethyl Alcohols: Structures,Oxidative Dearomatization and Chiroptical Properties

Chiral trifluoromethyl alcohol groups were introduced at the hindered ortho positions of 9,10-diphenylanthracenes to investigate their effects on the physical properties and reactivity towards oxidative dearomatization. In such compact structures, the position in different quadrants and the preferred orientation of the −CH(OH)CF₃ groups were determined by the relative and absolute configurations of each stereoisomer, respectively. As a consequence, the stereochemistry governs the organization of the H-bonded molecules in single crystals (homochiral dimers vs ribbon), whereas in chlorinated solvents, they all behave as discrete compounds. Concerning their reactivity, the stereospecific dearomative oxidation of these molecules leads to 9,10-bis-spiro-isobenzofuran-anthracenes, when using organic single-electron transfer oxidants. The chiroptical properties of the alcohols and the corresponding dearomatized products were compared and showed an important modulation of the intensity.     

Quantum chemical modeling of the reduction of cis-diammineplatinum(IV) tetrachloride [Pt(NH3)2Cl4] by methyl thiolate anion

We present here both an ab initio and quantum mechanical/molecular mechanical (QM/MM) study of the cis-[Pt(NH3)2Cl4] complex reduction by methyl thiolate anion, SCH(-3), which is used as a model of glutathione. Geometry and electronic structure of cis-[Pt(NH3)2Cl4] are determined without and in aqueous medium. The mechanism of the reaction of reduction is characterized. The calculated activation energy of the reaction compares remarkably well with the experimental value.     

On the interaction between supercritical CO2 and epoxides combining infrared absorption spectroscopy and quantum chemistry calculations

The nature and strength of the interactions occurring between epoxides and CO(2) have been investigated by combining infrared spectroscopy with quantum chemistry calculations. A series of infrared absorption experiments on four model epoxide molecules highly diluted in supercritical CO(2) have been performed at constant temperature T = 40 °C for various CO(2) pressures varying from 1 to 30 MPa. Then, we carried out a theoretical analysis based on quantum chemistry calculations using Density Functional Theory (B3PW91 and CAM-B3LYP) and ab initio (MP2) computational methods. A very good agreement between experimental and calculated vibrational frequency shifts of the epoxide ring vibrations group was obtained using the CAM-B3LYP functional, hence validating the calculated optimized geometries of the epoxide-CO(2) complexes. Whatever the epoxide considered, CO(2) is found to be on average above the oxygen atom of the epoxy ring and interacts with the carbon atom of CO(2) through a Lewis acid-Lewis base type of interaction. The substituents on the epoxide ring are found to influence the stability of the epoxide-CO(2) complexes mainly because of the partial charge on the oxygen atom that is sensitive to the nature of the substituent.     

Allylsilanes in "tin-free" oximation, alkenylation, and allylation of alkyl halides

Tin-free oximation, vinylation, and allylation of alkyl halides have been developed by using allylsilanes as di-tin surrogates. Initiation of the radical process with a peroxide provides the silyl radical, which can abstract a halogen from the corresponding alkyl halide. The resulting carbon-centered radical then adds to various acceptors, including a sulfonyloxime, a vinylsulfone, and an allylsulfone, leading to formation of the desired products along with the corresponding allylsulfone resulting from the reaction of the PhSO(2) radical with the allylsilane precursor. Better results were generally obtained with methallylsilane 1b than with 1a. This observation was rationalized by invoking the higher nucleophilicity of 1b and the faster β-fragmentation of the corresponding β-silyl radical intermediate. Calculation of the energy barrier for the β-fragmentation of a series of β-silyl radicals at the DFT level supported this hypothesis. Finally, a second version of these oximation and vinylation reactions, based on the utilization of 3-tris(trimethylsilyl)silylthiopropene, was devised, affording the desired oximes and olefins in reasonable yields. This strategy allowed the title reaction to be performed under milder conditions (AIBN, benzene, 80 °C), as a result of the easier β-fragmentation of the C-S bond as compared with the C-Si bond.