Non-oxo vanadium(IV) alkoxide chemistry: solid state structures, aggregation equilibria and thermochromic behaviour in solution

The reversible thermochromic behaviour of homoleptic [{V(OR)(4)}(n)] complexes in solution [R = Pr(i) (product I), Bu(s) (B(s)), Nep (N) and Cy (C)] is accounted for the existence of an aggregation equilibrium involving dimeric and monomeric species in which vanadium(iv) is respectively five- and four-coordinate. Bulky R groups such as Bu(t) and Pe(t) (tert-pentoxide) prevent aggregation and therefore give rise to exclusively mononuclear compounds (B(t) and P(t), respectively) that are not thermochromic. The complexes and their temperature-dependent interconversion were characterised by single crystal X-ray diffractometry, magnetic susceptibility measurements and electronic, FTIR and EPR spectroscopies in a wide temperature range. Equilibrium constants and enthalpy and entropy changes for the dimerization reactions have been determined and compared with literature data.     

Regioselective synthesis of isochromenones by iron(III)/PhSeSePh-mediated cyclization of 2-alkynylaryl esters

A series of 4-Se-(Te, S)-isochromenones and 3-substituted isochromenones were synthesized in good yields via FeCl(3)-mediated cyclization of alkynylaryl esters with different diorganyl dichalcogenides. This methodology was carried out at room temperature, using inexpensive and environmentally friendly iron salts as metallic source and under air atmosphere. The reaction showed to be tolerant to a range of substituents bonded into the aromatic ring of the diorganyl dichalcogenides as well as to alkyl groups directly bonded to the chalcogen atom. Alternatively, the cyclization reaction of 2-alkynylaryl esters with FeCl(3), in the absence of diorganyl dichalcogenide, gave the isochromenones without the chalcogen moiety in the structure. This approach proved to be highly regioselective, providing only six-membered ring products, once the possible five-membered products were not observed in any experiments.     

Increasing risk aversion and life-cycle investing

Mathematics and Financial Economics - We derive the optimal portfolio for an investor with increasing relative risk aversion in a complete continuous-time securities market. The IRRA assumption...     

Recent research using the Oxford electron beam ion trap

The presence of the σ-phase in Fe-Cr alloys (eg. Stainless steel) is important in industrial applications and from an academic point of view. The presence of the σ-phase in these alloys drastically affects their mechanical properties and their resistance to various corrosive media. In the present investigation Fe-Cr alloys containing different amounts of Mo were prepared and the transformation to the σ-phase was carried out by isothermally annealing the samples for various periods in an argon atmosphere. It will be shown that the presence of Mo has a dramatic accelerating effect on the rate of the σ-phase formation in these alloys. This revised version was published online in August 2006 with corrections to the Cover Date.     

Absolute rate constants for reactions of free radicals in the high-temperature photolysis of formamide vapor. II. Amino radicals

The rotating-sector method has been applied to the photoinitiated radical-chain decomposition of formamide at 300°C to measure the rate constant for the bimolecular disappearance of NH₂ radicals. The decomposition is propagated by the reactions (1) (2) Conditions were chosen so that reaction (1) was rate controlling and NH₂ the terminating radical. A flow system was employed with C₂F₆ as a carrier gas at a pressure of 300 Tort, and the chain reaction was initiated by the photolysis of either formamide or NH₃. A value of 4.7(±2.0) × 10¹⁰ (M ·sec)^?1 was estimated for the termination reaction (3) and a value of 8.4 × 10⁶ (M ·sec)^?1 for reaction (1) in the same system, both at 300°C.     

Rate constants for abstraction of hydrogen from ethylene by methyl and ethyl radicals relative to abstraction from propane and isobutane

A method is described for the measurement of relative rate constants for abstraction of hydrogen from ethylene at temperatures in the region of 750 K. The method is based on the effect of the addition of small quantities of propane and isobutane on the rates of formation of products in the thermal chain reactions of ethylene. On the assumption that methane and ethane are formed by the following reactions, (1) measurements of the ratio of the rates of formation of methane and ethane in the presence and absence of the additive gave the following results: Values for k₂ and k₃ obtained from these ratios are compared with previous measurements.     

Fission induced by heavy-ion collisions

Fission fragment angular distributions from sequential fission induced in heavy-ion reactions will depend on the angular momentum exchange occuring in such reactions in considerable detail. Theoretical expressions for the angular distributions of fission products from totally and partly polarized nuclei are presented. They are compared with recent measurements and discussed in relation to the deep inelastic reaction mechanism.     

Blitzlampe für Lichtpulse im Nanosekundenbereich

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