New chiral phosphine-phosphite ligands in the enantioselective palladium-catalyzed allylic alkylation

A series of chiral phosphine-phosphite ligands 1-6 have been synthesized and used in the enantioselective palladium-catalyzed reaction of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate as nucleophile. Ligands 1a, 2, 3, 5a, 6a, and 6b have been synthesized starting from racemic tert-butylphenylphosphinoborane. The use of dynamically resolved Li phosphide (-)-sparteine provided the optically pure ligands. Crystals of the allylpalladium (6a) complex were obtained, suitable for X-ray crystal structure determination. The X-ray crystal structure of the allylpalladium (6a) complex revealed a longer palladium-carbon bond distance trans to the phosphine moiety indicating that the attack of the nucleophile takes place at the carbon trans to the phosphine moiety. This was confirmed by the fact that the phosphine moiety did not affect the enantioselectivity directly. Under mild reaction conditions, enantioselectivities up to 83% were obtained (25 degrees C) with ligand 1e. Systematic variation of the ligand bridge and the phosphite moiety showed that the configuration of the product is controlled by the atropisomerism of the biphenyl substituent at the phosphite moiety. The conformation of the biphenyl group, in turn, is controlled by the substituent at the chiral carbon in the bridge. Ligands with large bite angles yielded higher enantioselectivities.     

Intercalation of Benzamide into Kaolinite

Well-crystallized kaolinite (K) was initially reacted at 60 degrees C with a water/dimethylsulfoxide (DMSO) mixture and the resulting intercalation derivative (K-DMSO) was characterized by powder X-ray diffractometry (PXRD), thermal analysis (simultaneous TG and DSC), and Fourier-transformed infrared spectroscopy (FTIR). Benzamide crystals were then melted with the K-DMSO derivative at 140 degrees C for 4 days, when a gradual displacement of DMSO by benzamide was observed within the interlayer spacing of the modified kaolinite. The resulting material, after extensive washing with acetone, was characterized and compared to the results obtained previously for the K-DMSO composite. Benzamide intercalation proceeded by gradual displacement of DMSO molecules until completion. The structural stabilization of the K-BZ derivative was explained through the establishment of hydrogen bonds between the carbonyl oxygen atoms of the intercalated benzamide and aluminol groups present at the surface of the kaolinite layer. The interlamellar spacing of K-BZ was shown to be possibly occupied by benzamide molecules that were located at a 68 degrees orientation in relation to the layer surface. Unlike most intercalation molecules such as DMSO, variations in the interplanar spacing of kaolinite were consistent with the nonkeying of any other part of the molecule between the aluminosilicate interlayers. Copyright 2000 Academic Press.     

Green's function of radial inhomogeneous spheres excited by internal sources

Green's function in the interior of penetrable bodies with inhomogeneous compressibility by sources placed inside them is evaluated through a Schwinger-Lippmann volume integral equation. In the case of a radial inhomogeneous sphere, the radial part of the unknown Green's function can be expanded in a double Dini's series, which allows analytical evaluation of the involved cumbersome integrals. The simple case treated here can be extended to more difficult situations involving inhomogeneous density as well as to the corresponding electromagnetic or elastic problem. Finally, numerical results are given for various inhomogeneous compressibility distributions.     

Population of the states in collisions of mixed-state (1s21S,1s2s3S) B3+ and C4+ ion beams with He and H2 targets

Auger KLn lines are observed in high-resolution electron spectra obtained in collisions of mixed-state (1s²¹S,1s2s³S) He-like beams of 4 MeV B³⁺ with H₂ and 6 MeV C⁴⁺ with He targets. Supporting atomic structure calculations show these lines to correspond to doubly excited states, which can be readily populated by electron transfer to the component of the mixed-state beam. They thus provide indirect evidence for the existence of the corresponding KLn quartet states, similarly produced, even though their weak Auger decay does not allow for their direct observation in the electron spectra. These KLn quartet states mostly decay in a cascade chain of strong radiative E1 transitions, eventually terminating at the state, which is thus additionally enhanced. An upper limit on the state population due to cascades is obtained by assuming a statistical production of KLn quartet to doublet states followed by a 100% cascade feeding of the state. Our estimated upper limit is supported by our absolute cross section measurements and corresponding three-electron atomic orbital close coupling calculations in progress. Results to date are presented and discussed.     

Effect of viscous dissipation on the mixed convection heat transfer from an exponentially stretching surface

The mixed convection flow and heat transfer from an exponentially stretching vertical surface in a quiescent fluid is analyzed using similarity solution technique. Wall temperature and stretching velocity are assumed to have specific exponential function forms. The influence of buoyancy along with viscous dissipation on the convective transport in the boundary layer region is analyzed in both aiding and opposing flow situations. The flow is governed by the mixed convection parameter Gr/Re². The velocity and temperature inside the boundary layer are observed to be influenced by the parameters like Prandtl number Pr, Gebhart number Gb. Significant changes are observed in non-dimensional skin friction and heat transfer coefficients due to viscous dissipation in the medium. The flow and temperature distributions inside the boundary layer are analyzed and the results for non-dimensional skin friction and heat transfer coefficients are discussed through computer generated plots.     

Instabilities of massive scalar perturbations of a rotating black hole

We study the stability of a massive scalar field in the exterior metric of a rotating Kerr black hole. An argument based on energy conservation shows, under some strong technical assumptions, that unstable normal modes exist. These unstable modes can be interpreted as wave packets in bound, superradiant orbits. A JWKB estimate of the fastest growth rate gives 10^?7M^?1exp(?1.84Mμ) in the case Mμ ? 1, where M is the mass of the hole and μ is the mass of the field. The existence of unstable normal modes has significant implications for quantum particle creation by rotating black holes, which we attempt to assess.     

Fringing field optimization of hemispherical deflector analyzers using BEM and FDM

In this paper we present numerical modeling results for fringing field optimization of hemispherical deflector analyzers (HDAs), simulated using boundary-element and finite-difference numerical methods. Optimization of the fringing field aberrations of HDAs is performed by using a biased optical axis and an optimized entry position offset (paracentric) from the center position used in conventional HDAs. The described optimization achieves first-order focusing thus also further improving the energy resolution of HDAs.