Shear flow experiments in an assembly of gel beads and modelling of bingham behavior

In this paper, we present a rheological study of a compact layer of highly swollen gel beads. The flow regimes of these systems are modelled by an elastic sinusoid moving in a Newtonian fluid. This model predicts a yield stress varying with the square root of the elastic modulus of the gel bead. The slope at the origin (at zero velocity) of the flow curve is expected to depend only on geometrical parameters and on the solvent viscosity. The experimental data are in qualitative agreement with the theoretical predictions.     

Analysis of polyaddition levels in i-Sc3NC80

Using the density functional method, the stabilities of highly hydrogenated and fluorinated [80]fullerenes, both empty and containing the Sc3N molecule, have been calculated. Addition of 44 atoms to i-Sc3NC80 is predicted to be most favorable due to the formation of six octahedrally located benzenoid rings, while addition of up to 52 atoms (consistent with preliminary fluorination data) gives a structure stabilized by the presence of four benzenoid rings. The most stable isomers at this addition level have been determined and the relative stabilities of a number of C80H52, C80F52, and i-Sc3NC80H52 species calculated. The hydrogenation of the i-Sc3NC80 has been computed to be more difficult than the corresponding partner, C80. From the geometrical point of view, the Sc3N molecule is planar in the parent [80]fullerene but is calculated to be pyramidal in some of the hydrogenated/fluorinated derivatives. Moreover, in these it has fixed locations due to orbital interactions arising from deformation of the cage and the presence of localized double bonds.     

Préparation,configuration et réduction électrochimique d'α-cyano β-nitrostyrènes. Synthèse d'amino-5 isoxazoles

Z α-Cyano-β-nitrostyrenes were prepared by nitration with dinitrogentetroxide of the corresponding α-cyanostyrenes. Elsomers were obtained by photoirradiation of Z isomers. The electrochemical reduction of these cyanonitro compounds generates the α-cyanooximes which lead, according to the experimental conditions(ring closure or hydrolysis), either to 5-aminoisoxazoles or to β-ketonitriles.     

Metal ion complexes of 2-picolinamineN-oxide

Summary A series of cobalt(II), nickel(II) and copper(II) complexes of 2-picolinamineN-oxide, HA, has been prepared. Solids of formula [M(HA)₃](BF₄)₂ (M=cobalt(II) or nickel(II); [Cu(HA)₂]X₂ (X=BF ₄ ^– , NO ₃ ^– ); [Co(HA)₂X₂] (X=Cl^– or Br^–); [Ni(HA)₂Cl₂] and [Cu(HA)X₂] (X=Cl^– or Br^–] have been isolated and characterized by partial elemental analyses, molar conductivities, magnetic susceptibilities, DSC-TGA, and spectral methods. All complexes were found to be monomeric, and their spectral parameters are compared with those of the metal ion complexes ofN-alkyl-2-picolinamineN-oxides, 2-dialkylaminopyridineN-oxides and 2-picolinamine. The cobalt(II) and nickel(II) halide complexes spectrally show a mixture of octahedral and tetrahedral centres.     

A Convergent Synthesis of (±)-α- and β-Himachalenes

(±)-α and β-Himachalene, 5 and 6 , have been synthesized in a convergent manner from 3,3-dimethylacrolein ( 9 ), the ester enolate 10 and the silyloxypentadienyllithium 7 . The key steps are the regioselective γ-addition of the dienal 13 to 7 and the intramolecular Diels-Alder addition 15 → 16 . Hydrogenolysis of the diethylphosphate group and functionalization at C (5) completed the synthesis of 5 and 6 .     

Metal ions in biological systems, vol. 2, metal ligand complexes : ed. by H. Sigel, Dekker, New York, 1973, xiv + 294 pages, $25.25

The kinetic isotope effect for β-hydride elimination from alkyliridium(I) complexes has bee found to be k_H/k_D = 2.28 ± 0.20.     

Bimetallic reactivity. One-site addition two-metal oxidation reaction of dioxygen with a bimetallic dicobalt(II) complex bearing five- and six-coordinate sites

The di-Co(2+) complex, [Co(2+)(mu-OH)(oxapyme)Co(2+)(H(2)O)](+), contains an unsymmetrical binucleating ligand (oxapyme) which provides five- and six-coordinate metal sites when a hydroxide bridge is introduced. This complex absorbs 1 equiv of O(2) irreversibly in solution, producing an unstable di-Co(3+) oxygenated product. The oxygenated product has been studied at low temperatures, where its electronic absorption and (1)H NMR spectra were recorded. It is probable that the oxygenation reaction involves a one-site addition two-metal oxidation reaction to produce an end-on-bonded peroxide ligand at the available coordination site, giving the complex [Co(3+)(mu-OH)(oxapyme)Co(3+)(mu(1)-O(2))](+). Addition of 1 equiv of HClO(4) to this oxygenation product gives a stable peroxide complex, [Co(3+)(mu,eta(1):eta(2)-O(2))(oxapyme)Co(3+)](2+), where one of the oxygen atoms bridges the two metals and is sideways bonded to one of the metals. The formation of this stable complex involves expulsion of the OH(-) bridge. Addition of NO(2)(-) to the sideways-bonded peroxide complex leads to the formation of another stable complex, [Co(3+)(mu,eta(1):eta(1)-O(2))(oxapyme)Co(3+)(NO(2))](+), where the peroxide forms a classic di-end-on bridge to the two metals. Both of these complexes have been fully characterized. Addition of acid to this second stable dioxygen complex leads to the release of HNO(2) and the formation of the mu,eta(1):eta(2) sideways-bonded peroxide complex.     

Isobutane chemical ionization mass spectra of unsaturated alcohols

Analysis of the isobutane chemical ionization mass spectra of hexenols, cyclohexenols and various syn/anti pairs of bicyclic and tricyclic homoallylic alcohols shows that: (i) the spectra of the allylic alcohols are dominated by [M + H – H₂O]⁺ and [M + C₄H₉–H₂O]⁺ ions and contain traces of [M + H]⁺ ions; (ii) [M + H]⁺ ions are prominent in the spectra of acyclic and certain cyclic homoallylic alcohols; and (iii) [M + H]⁺ ions dominate the spectra of other acyclic unsaturated alcohols. The [M + H]⁺ ions may result from either: (a) protonation of the hydroxyl group, followed by a very rapid intramolecular proton transfer from the protonated hydroxyl group to the carbon–carbon double bond or internal solvation of the protonated hydroxyl group by the carbon–carbon double bond; and/or (b) direct protonation of the carbon–carbon double bond with significant internal solvation of the resulting carbocation by the hydroxyl group, which may lead to carbon–oxygen bond formation to give a protonated cyclic ether. The consequences of placing various geometric constraints on the possible intramolecular interactions between the hydroxyl group and the carbon–carbon double bond in unsaturated alcohols are explored.     

Preparation and electrochemical behavior of dimeric complexes of Ru2(III12, III12) and Ru2(IV,IV) formed by oxidative dimerization of [RuIII(edta)OH2]−

Electrochemical or chemical oxidation of [Ru^III(edta)OH₂]^? proceeds in successive half- and one-electron steps to yield dimeric complexes of Ru(III$\text{1}\text{2}$) and Ru(IV) believed to contain oxo- or dihydroxo-bridging ligands. Spectral and electrochemical properties of the complexes prepared by oxidative dimerization are described and compared with previous reports of dioxygen and peroxo complexes of Ru^III(edta). The dimeric Ru^IV(edta) complex is shown to exhibit modest activity as a catalyst for the oxidation of water to dioxygen.