Molybdenum amido complexes with single Mo-N bonds: synthesis,structure, and reactivity

Reactions of the complex [MoCl(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)] (1) (phen=1,10-phenanthroline) with potassium arylamides were used to synthesize the amido complexes [Mo(N(R)Ar)(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)] (R=H, Ar=Ph, 2 a; R=H, Ar=p-tolyl, 2 b; R=Me, Ar=Ph; 2 c). For 2 b the Mo-N(amido) bond length (2.105(4) A) is consistent with it being a single bond, with which the metal attains an 18-electron configuration. The reaction of 2 b with HOTf affords the amino complex [Mo(eta(3)-C(3)H(4)-Me-2)(NH(2)(p-tol))(CO)(2)(phen)]OTf (3-OTf). Treatment of 3-OTf with nBuLi or KN(SiMe(3))(2) regenerates 2 b. The new amido complexes react with CS(2), arylisothiocyanates and maleic anhydride. A single product corresponding to the formal insertion of the electrophile into the Mo-N(amido) bond is obtained in each case. For maleic anhydride, ring opening accompanied the formation of the insertion product. The reaction of 2 b with maleimide affords [Mo(eta(3)-C(3)H(4)-Me-2)[NC(O)CH=CHC(O)](CO)(2)(phen)] (7), which results from simple acid-base metathesis. The reaction of 2 b with (p-tol)NCO affords [[Mo(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)](2)(eta(2)-MoO(4))] (8), which corresponds to oxidation of one third of the metal atoms to Mo(VI). Complex 8 was also obtained in the reactions of 2 b with CO(2) or the lactide 3,6-dimethyl-1,4-dioxane-2,5-dione. The structures of the compounds 2 b, 3-OTf, [Mo(eta(3)-C(3)H(4)-Me-2)[SC(S)(N(H)Ph)](CO)(2)(phen)] (4), [Mo(eta(3)-C(3)H(4)-Me-2)[SC(N(p-tol))(NH(p-tol))](CO)(2)(phen)] (5 a), and [Mo(eta(3)-C(3)H(4)-Me-2)[OC(O)CH=CHC(O)(NH(p-tol))](CO)(2)(phen)] (6), 7, and 8 (both the free complex and its N,N'-di(p-tolyl)urea adduct) were determined by X-ray diffraction.     

Hartree-Fock energy partitioning in terms of Hirshfeld atoms.

A Hirshfeld decomposition scheme of the Hartree-Fock total molecular energy into atomic energies is presented. The calculations are performed by direct numerical integration and the results are compared for a set of 28 molecules containing different kinds of atoms. The calculated atomic energies show a strong dependency on changes of atomic electron population and hybridization. Linear correlations are found between the energy and the population for H, these being related to the electronegativity of this atom and to the external potential created by the remaining atoms. The proposed energy partitioning scheme appears to be useful for studies such as proton acidity, the anomeric effect and group transferability, and allows atomic virial ratios to be obtained. Finally, the atomic potential energies are found to mimic trends based on exact expressions as well as trends displayed by molecular quantities, thus lending credibility to the partitioning scheme used.     

Strongest gravitational waves from neutrino oscillationsat supernova core bounce

Resonant active-to-active ( ), as well as active-to-sterile ( ) neutrino ( ) oscillations can take place during the core bounce of a supernova collapse. Besides, over this phase, weak magnetism increases the antineutrino ( ) mean free path, and thus its luminosity. Because the oscillation feeds mass-energy into the target species, the large mass-squared difference between the species ( ) implies a huge amount of energy to be given off as gravitational waves ( erg s^-1), due to anisotropic but coherent flow over the oscillation length. This asymmetric -flux is driven by both the spin-magnetic and the universal spin-rotation coupling. The novel contribution of this paper stems from (1) the new computation of the anisotropy parameter -0.01, and (2) the use of the tight constraints from neutrino experiments as SNO and KamLAND, and the cosmic probe WMAP, to compute the gravitational-wave emission during neutrino oscillations in supernovae core collapse and bounce. We show that the mass of the sterile neutrino that can be resonantly produced during the flavor conversions makes it a good candidate for dark matter as suggested by Fuller et al. , Phys. Rev. D 68, 103002 (2003). The new spacetime strain thus estimated is still several orders of magnitude larger than those from diffusion (convection and cooling) or quadrupole moments of neutron star matter. This new feature turns these bursts into the more promising supernova gravitational-wave signals that may be detected by observatories as LIGO, VIRGO, etc., for distances far out to the VIRGO cluster of galaxies.Received: 26 November 2003, Revised: 26 February 2004, Published online: 3 June 2004     

A note on coalitional manipulation and centralized inventory management

In this note we deal with inventory games as defined in Meca et al. (Math. Methods Oper. Res. 57:483–491, 2003). In that context we introduce the property of immunity to coalitional manipulation, and demonstrate that the SOC-rule (Share the Ordering Cost) is the unique allocation rule for inventory games which satisfies this property. The authors acknowledge the financial support of Ministerio de Educación y Ciencia, FEDER and Xunta de Galicia through projects SEJ2005-07637-C02-02 and PGIDIT06PXIC207038PN.     

Changes in the structure of composite colloid-polymer xerogels after cold isostatic pressing

Monolithic gels, prepared from different mixtures of colloidal silica in a sol solution containing tetraethoxysilane under powerful ultrasonic agitation (sonosols), were compacted at an isostatic pressure of 390 MPa. Then N₂ adsorption-desorption data were used to construct structural models of the gels using Monte-Carlo calculations on the basis of random close-packing (RCP) premises. Structural information on these composites obtained before compaction indicates that the characteristic uniform structure of silica colloid gel undergoes profound modification when it is mixed with silica sonogel. From a structural point of view, the behaviour under compaction of the sonogel phase, which exhibits a significant degree of microporosity, depends on the relative concentration of the colloidal phase. Two hierarchic levels of micropores were discerned. After compression, the size of the elementary particles—and their aggregates—of the sonogel phase increases from 1.6 to 2.1 nm radius when the colloidal phase content is increased from 30 to 82% by weight. For an intermediate content, 50% of the volume reduction is caused by compression of the sonogel phase at the micropore level.     

Nature of the intermediates in gold(I)-catalyzed cyclizations of 1,5-enynes

The carbene or carbocationic nature of the intermediates in the gold-catalyzed cycloisomerization of 1,5-enynes can be revealed, depending on the ligands on the gold catalysts. Gold complexes with highly electron-donating ligands promote reactions that proceed via intermediates with carbene-like character, leading to products with a bicyclo[3.1.0]hexene skeleton. The intermediate cyclopropyl endo-gold carbenes formed in this cyclization have been trapped, for the first time, to give biscyclopropane derivatives in a reaction that proceeds in a concerted fashion, according to DFT calculations.     

Design of insurance contracts using stochastic programming in forestry planning

This work addresses a tactical planning problem faced by a forestry firm, deciding which timber units to harvest and what roads to build to obtain the greatest possible benefits. We include uncertainty in prices by means of utility theory. This enables solutions to be found that the firm finds preferable to those obtained when risk aversion is ignored and makes it possible to design insurance contracts that benefit the firm while also being attractive to an insurer. Two types of contract are designed; one dependent on the firm’s operating result and the other independent of it. Metrics are then developed to quantify the benefits conferred by a contract, demonstrating that the latter contract type dominates the former. These results are then illustrated by applying them to a simplified planning problem of a forest owned by the Chilean forestry operator Millalemu.     

Influence of the solvent on the charge distribution of anomeric compounds

Conformational preferences of methanediol, dimethoxymethane, methanediamine, and fluoromethanol in the presence of solvents of diverse polarity (water, acetone, and chloroform), modeled with the polarizable continuum model, were analyzed within the framework of the Quantum Theory of Atoms in Molecules. The results indicate that the hydrogens bonded to the anomeric carbon experience the largest reorganization of electron density upon conformational change, as was obtained from previous calculations in the gas phase. When the water solvation is simulated by explicit inclusion of water molecules, the electron density reorganization involved in the cluster formation is significantly different for each conformer of methanediol. As a consequence, similar depletions of electron population are displayed by the hydrogens of hydroxyl and methylene groups in the cluster obtained for the most stable conformer of methanediol, with regard to that built for the completely antiperiplanar conformer.