Diastereoisomerically selective enantiomerically pure titanium complexes of Salan ligands: synthesis, structure, and preliminary activity studies

The degree of diastereoselectivity in the wrapping of four new chiral Salan ligands to form chiral-at-metal titanium complexes ranged from mild to perfect as a function of the ligands' N substituents; the enantiomerically pure complexes catalyzed the addition of diethyl zinc to benzaldehyde in 73-76% enantiomeric excess.     

Vanadium(III) and vanadium(V) amine tris(phenolate) complexes

The coordination chemistry of amine tris(phenolate) ligands around V(III) and V(V) is described for the first time. Three amine tris(phenolate) ligands were employed featuring different steric and electronic influence exerted by the phenolate substituents in the ortho and para positions being either t-Bu, Me, or Cl. V(III) complexes of all ligands (1-3) were readily obtained by reaction between the ligand precursors and VCl3(THF)3 in the presence of triethylamine. The complexes obtained were pentacoordinate, a THF ligand completing the coordination sphere of the metal, which was found to be of almost perfect TBP geometry, as revealed by crystallography. V(V) oxo complexes of all the ligands (4-6) were readily obtained by a reaction between the ligand precursors and VO(OPr)3. The oxo complexes of the alkyl-bearing ligands (4 and 5) could also be synthesized by the air oxidation of the corresponding V(III) complexes (1 and 2); however, the attempted air oxidation of the V(III) complex bound to the electron-poor ligand (3) did not yield the corresponding oxo complex 6. 1H NMR and crystallographic analysis of complexes 4 and 5 supported their TBP structures. Complex 6, on the other hand, was found to be composed of a TBP complex (6a) and an octahedral complex (6b) in equilibrium, the octahedral complex being more stable at lower temperatures. An X-ray structure of 6b revealed a mononuclear oxo complex, the sixth coordination site being occupied by an aqua ligand to which two THF molecules are H-bonded. Complexes 4-6 catalyze the epoxidation of olefins by t-BuOOH, albeit slowly. These complexes may thus be considered as structural and functional models of vanadium-dependent haloperoxidase enzymes.     

Phase transition in the fine structure constant

Within the context of mass-varying neutrinos, we construct a cosmological model that has a phase transition in the electromagnetic fine structure constant at a redshift of 0.5. The model accommodates hints of a time variable in quasar spectra and the nonobservance of such an effect at very low redshifts. It is consistent with limits from the recombination and primordial nucleosynthesis eras and is free of instabilities.     

Scaling in soft hadroproduction by positive projectiles in the range of 32–147 GeV/c

The total hadron multiplicity and the multiplicity in the three-jet events ine ⁺ e ^?-annihilation are considered. The formula for the total multiplicity (with account for the heavy quark contribution) agrees well with experiment. The value of the multiplicity for three-jet events is predicted.     

Novel ring-cleaving reaction of 4-nitro-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane with nucleophiles

When 4-nitro-AF4 is treated with nucleophiles such as alkoxides and cyanide, a novel ring opening, cyclophane destroying reaction is observed whereby, via an S_NAr mechanism, the nucleophile attacks the bridgehead aryl carbon vicinal to the nitro group with subsequent aryl-CF₂ bond cleavage.     

Chemiefreie Haushaltsprodukte

We have examined and subjected to analysis an exhaustive number of consumer products, including but not limited to lotions and cosmetics, herbal supplements, household cleaners, food items, and beverages. As a result we describe all those consumer products herein, to our knowledge, that are appropriately labelled as “Chemical free”.     

Cluster states in the neutron excess nucleus 22Ne

High-spin states of the ²²Ne nucleus in the excitation energy range of 15–30 MeV have been studied. The angular correlation method has been used to determine the spins of excited states. A number of new states with high angular momenta—20.0 MeV (9^?), 20.7 MeV (11^?), 21.6 MeV (9^?), 22.2 MeV (12⁺), and 25.0 MeV (9^?)—have been revealed. They are intensely populated in the reaction ¹⁴C(¹²C, α₁)²²Ne* → α₂ + ¹⁸O and correspond to the rotational bands of various structures.     

Electron capture and loss in the scattering of H+ from HOPG graphite

In this paper we report measurements of the positive (H⁺) and negative (H^?) ion fractions after H⁺ scattering from a highly oriented pyrolytic graphite (HOPG) surface. The experimental results show that for a fixed (large) exit angle the negative fraction is almost independent of the primary ion energy, while the positive fraction increases steadily. For a fixed incident energy, the H⁺ and H^? fractions show a complementary behavior with exit angle. A dynamical quantum mechanical calculation, based on the localized and extended features of the atom–surface interaction, allows us to understand many of the features of the experimental results.     

Geodesic Webs on a Two-Dimensional Manifold and Euler Equations

We prove that any planar 4-web defines a unique projective structure in the plane in such a way that the leaves of the web foliations are geodesics of this projective structure. We also find conditions for the projective structure mentioned above to contain an affine symmetric connection, and conditions for a planar 4-web to be equivalent to a geodesic 4-web on an affine symmetric surface. Similar results are obtained for planar d-webs, d>4, provided that additional d−4 second-order invariants vanish.     

Stable Subnorms II

In this paper we continue our study of stability properties of subnorms on subsets of finite-dimensional, power-associative algebras over the real or the complex numbers.