Etude de la tétracoordination de l'etain dans deux orthothiostannates: Na4SnS4 et Ba2SnS4 (α)

The crystal structure of Na₄SnS₄ and Ba₂SnS₄ (α) were determined.Na₄SnS₄ crystallizes in tetragonal system, space group $\text{P}\text{4}\text{2}{}_1\text{c}$ with parameters a = 7.837 Å, c = 6.950 Å, Z = 2 and Ba₂SnS₄ (α) in the monoclinic system, space group $\text{P2}{}_1\text{c}$ with a = 8.481 Å, b = 8.526 Å, c = 12.280 Å, β = 112.97° and Z = 4.In these compounds, the crystal structure is built up from discrete orthothiostannate tetrahedra SnS₄. The structure of Ba₂SnS₄ (α) is modified K₂SO₄β type.     

Sol–Gel Derived Organic and Inorganic Hybrid Materials for Photonic Applications: Contribution to the Correlation Between the Material Structure and the Transmission in the Near Infrared Region

A promising way of fabricating integrated optics components is based on the sol–gel synthesis and photocuring of organic-inorganic hybrid materials. However, the main factor limiting the development of passive devices is the propagation losses. Moreover, the possibility to compensate these attenuations by optical amplification is competed with the multiphonon relaxation associated to the presence of OH groups. To our knowledge, OH groups were always shown as the main responsible for attenuation at the telecommunication wavelengths, namely at 1310 and 1550 nm, although the matrix is composed of organic species which can contribute to absorptions in this spectral range. This paper deals with spectroscopic and optical characterizations of a well established organic and inorganic hybrid material in order to determine the contribution of each molecular groups to the attenuation at the aforementioned wavelengths.     

Solvent-controlled additions of organotitanium reagents to olefinic double bonds

Under carefully chosen working conditions (solvent, temperature), methyltitanium reagents smoothly convert homoallyl alcohols having a terminal double-bond into (E)-3-penten-l-ols whereas non-terminal 3-alken-l-ols afford 4-methyl-branched derivatives with configurational inversion of the chain (Z → E; E → Z), stereoselectivities being better than 99%.     

The high-valent iron-oxo species of polyoxometalate, if it can be made, will be a highly potent catalyst for C-H hydroxylation and double-bond epoxidation

This study uses density functional theory (DFT) calculations to explore the reactivity of the putative high-valent iron-oxo reagent of the iron-substituted polyoxometalate (POM-FeO4-), derived from the Keggin species, PW12O40(3-). It is shown that POM-FeO4- is in principle capable of C-H hydroxylation and C=C epoxidation and that it should be a powerful oxidant, even more so than the Compound I species of cytochrome P450. The calculations indicate that in a solvent, the barriers, and especially those for epoxidation, become sufficiently small that one may expect an extremely fast reaction. An experimental investigation (by R.N. and A.M.K.) shows, however, that the formation of POM-FeO4- using the oxygen donor, F5PhI-O, leads to a persistent adduct, POM-FeO-I-PhF5(4-), which does not decompose to POM-FeO4- + F5Ph-I at the working temperature and exhibits sluggish reactivity, in accord with previous experimental results (Hill, C. L.; Brown, R. B., Jr. J. Am. Chem. Soc. 1986, 108, 536 and Mansuy, D.; Bartoli, J.-F.; Battioni, P.; Lyon, D. K.; Finke, R. G. J. Am. Chem. Soc. 1991, 113, 7222). Subsequent calculations indeed reveal that the gas-phase binding energy of F5PhI to POM-FeO4- is high (ca. 20 kcal/mol) compared to the corresponding binding energy of propene (ca. 2-3 kcal/mol). As such, the POM-FeO-I-PhF5(4-) complex is expected to be persistent toward the displacement of F5PhI by a substrate like propene, leading thereby to sluggish oxidative reactivity. According to theory, overcoming this technical difficulty may turn out to be very rewarding. The question is, can POM-FeO4- be made?     

Diphasic Domains Approach Method (DDAM)

If someone wants to plot an isobaric temperature-composition binary or an isobarothermal section of a ternary equilibria phase diagram he only needs to plot the limits of diphasic domains, it automatically gives the limits of the monophasic and triphasic fields. In such diagrams each diphasic domain is defined by two lines joining all the extremities of the tie-lines of the domain and limited by the first and the last one. These tie-lines are segments whose the extremities are in the plane of the diagram and can easily be determined by equilibria calculation codes. Then binary or ternary phase diagrams can be plotted only using conodes of the diphasic fields and the method used to determine the diphasic domains becomes the main point in binary and ternary phase diagrams plotting. A meshing of the surface of the diagram is certainly not the best way to obtain a rapid result. We propose an approach which consists to follow the curvature of the diphasic domains limits, the ‘Diphasic Domains Approach Method, DDAM’, which allows a rapid and robust determination of binary and ternary diagrams.     

Direct-type catalytic three-component Mannich reaction in aqueous media

Bismuth triflate catalyzed direct-type Mannich reaction of cyclohexanone, aromatic aldehyde, and aromatic amine proceeded smoothly in water to afford the corresponding β-amino ketone with very good yield and moderate to good anti selectivity.