A facile synthesis of substituted benzyl selenocyanates

Benzyl selenocyanates can be made from the corresponding benzylic bromides or chlorides in 30-60 minutes using acetonitrile as a solvent. The products may be obtained pure in satisfactory yields without recourse to chromatography.     

Laser thermal response of a finite slab as a function of the laser pulse parameters

This paper deals with the problem of heating a finite slab using laser radiation in relation to the parameters characterizing the laser pulse, namely: q_max(W/m²), the maximum laser power density, t₀ the time interval required to reach q_max and t_d, the pulse time duration. The pulse shape q(t) is suggested in the form: q(t)=βq_max(t/t_d)(1-(t/t_d))exp-B(t-t₀/t_d), where β and B are parameters. Fitting with published experimental pulse [Ready JF. Effects due to absorption of laser radiation. J Appl Phys 1965;36:462–68] is made. Fourier series expansion technique is considered to solve the problem. The critical time required to initiate melting t_m is estimated for four metallic elements and five semiconductors, namely: Al, Cu, Ag, Au (aluminum, copper, silver, and gold), cadmium sulfide, germanium, silicon, alpha beryllium oxide, and silicon carbide. Five pulses with different characteristic parameters are considered.Computations revealed that the thermal response of the targets is highly affected by q_max and t_o, while the pulse time duration is less effective in determining the value of t_m. Moreover, it is revealed that the relation between t_m and the melting temperature for the same laser pulse is nonlinear for the considered targets under the indicated conditions.     

Primary products and mechanistic considerations in alkane metathesis

Alkane metathesis, a reaction catalyzed by the silica-supported tantalum hydride [(SiO)2Ta-H], 1, which transforms acyclic alkanes into their higher and lower homologues, was reported in 1997. New studies conducted in a continuous flow reactor in the case of propane indicate that, by varying the contact time, hydrogen and olefins are primary products. This crucial observation, as well as the known properties of tantalum alkyls to perform alpha-H or beta-H eliminations, supports the proposition of a new mechanism involving metallacyclobutane intermediates just like in olefin metathesis. The observed selectivities for linear and branched Cn+1 and Cn+2 products as well as the linear/branched ratio can be well-explained on the basis of the minimization of steric interactions between 1,2- or 1,3-substituents in the various tantallacyclobutane intermediates or during their formation. Hydrogen plays a specific role in the cleavage of metal alkyls to complete the catalytic cycle.     

Porous lanthanide-organic framework with zeolite-like topology

Two novel isomorphous porous frameworks of Ln(III), {[Ln2(imidc)2(H2O)3](H2O)}n, [Ln = Gd(III) (1) and Er(III) (2)] have been synthesized hydrothermally using multifunctional 4,5-imidazoledicarboxylic acid (imidc) as a connector; they have a zeolite-like network topology which can provide another form upon dehydration, and exhibit selective adsorption properties for H2O over N2, CO2 and MeOH.     

Molybdenum and tungsten complexes of biquinoline. Crystal structure of W(CO)4(2,2′-biquinoline)

M(CO)₆ (M = Mo and W) reacts with 2,2-biquinoline (biq) to yield tetracarbonyl derivatives M(CO)₄(biq). Crystals suitable for X-ray structure determination of W(CO)₄(biq) were isolated from benzene solution. The u.v.–vis. spectra of the complexes exhibited visible transitions due to metal-to-ligand charge-transfers. Electrochemical investigation of the complexes showed some irreversible, reversible and quasi-reversible redox reactions due to tautomeric interconversions through electron transfer. The thermal properties of the complexes were also investigated using the thermogravimetric technique.     

A nonlinear problem having a continuous locus of singular points and no multiple solutions

The boundary-value problem ?z″ = (z² ? t²)z′, ? > 0, z(? 1) = α, z(0) = β, t? [?1, 0], has been shown to have a solution, and moreover, depending on the choice of α and β, multiple solutions to it exist. We consider the more general equation f(z, t)z″ = (z^r ? t^s)z′ for a particular non-negative function f(z, t), and integrate the equation exactly. Depending on α and β, we find that either there are no solutions, or that only unique solutions exist. The conclusion is that the presence of a continuous locus of singular points, given by z^r = t^s, does not necessarily produce multiple solutions.     

NMR studies in the heterocyclic series. XVIII—Carbon-13 NMR study of azolium salts. Attempted correlation of chemical shifts with calculated charge densities

The carbon-13 chemical shifts and the ¹J(CH) coupling constants for 18 azolium salts (di-N-methyl-pyrazolium, -indazolium, -benzimidazolium and -benzotriazolium iodides) have been determined and assigned. The chemical shifts are discussed as a function of substituent effects, positive charge introduction and total electronic density (calculated by the CNDO/2 method). The general problem of correlations between chemical shifts and total charge densities in azoles is discussed. A statistical approach shows that these correlations are of poor quality.