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.     

Unfolding of an unstable singularity point into a ring

It is well known that phase singularities, in general lines in space, are topologically stable features of a wave field. An exception is a pointlike singularity, which is unstable and deforms into a ring or disappears when a small perturbation is applied. Recently, Nye showed how such an event can be understood as an unfolding of a higher-order dislocation [J. Opt. Soc. Am. A (to be published)]. We present an optical implementation of this model and show experimentally that the focal region of a lens contains points of zero intensity on the optical axis that deform into rings when a small amount of spherical aberration is applied to the system.     

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.     

Synthesis,spectroscopic characterization and catalytic activity of cis-dioxidomolybdenum (VI) complexes with chiral tetradentate Schiff bases

New chiral mononuclear cis-dioxidomolybdenum (VI) complexes, MoO ₂ L ¹ –MoO ₂ L ¹⁰ , with tetradentate Schiff bases derived from various substituted salicylaldehydes and 1S,2S-(+)-2-amino-1-(4-nitrophenyl)-1,3-propanediol were synthesized. All complexes were characterized by elemental analysis, circular dichroism, electronic and IR spectroscopy. ¹H NMR and also two-dimensional (COSY, NOESY and gHSQC) NMR measurements made for MoO ₂ L ¹ –MoO ₂ L ¹⁰ complexes show that Schiff bases are coordinated to the MoO₂²⁺ cation, creating facial (fac) and meridional (mer) types of geometrical isomers. Moreover, catalytic activity studies were also performed for all complexes in asymmetric sulfoxidation of thioanisole and epoxidation of styrene, cyclohexene and two monoterpenes, i.e. S(−)-limonene and (−)-α-pinene, using aqueous 30% H₂O₂ or tert-butyl hydroperoxide as the oxygen source.     

Fractal structure of eigenmodes of unstable-cavity lasers

We show that the eigenmodes of unstable-cavity lasers have fractal structure, in contrast with the well-known stable-cavity eigenmodes. As with all fractals, the dynamic range over which self-similarity holds is limited; in this case the range is set by diffraction, i.e., by the Fresnel number of the resonator. We determine the fractal dimension of the mode profiles and show that it is related to the aperture shape.     

Creation and annihilation of phase singularities in a focal field

It is well known that uniform illumination of a lens leads to a focal field with a pattern of dark Airy rings in the focal plane, whereas this is not the case for Gaussian illumination. We show theoretically and experimentally that in the transition between the two cases the Airy rings, being phase singularities, reorganize themselves by means of a creation-annihilation process leading to new dark rings outside the focal plane.     

Magnetic properties of TlCaBaCuO4.5 compounds prepared from different starting materials

It has been shown, that different starting materials result in Tl–Ca–Ba–Cu–O superconductors of different type even at the same heat treatment process. This manifests itself in the developing structure, in the number, share-rate and superconducting properties of the occurring phases as well. Microcrystals, phase-compositions, crystallinities, unit cells, onset and critical temperatures, magnetic flux exclusions, critical currents, magnetizations and critical magnetic fields essentially unlike from each other have been observed, depending on the starting materials. The presence of a starting compound having low melting point, as Ba(NO₃)₂ can cause a more compact, better superconducting final product, implying better connection between the grains.     

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.     

Observed factorization of excess quantum noise that is due to both polarization and spatial mode nonorthogonality

When the eigenmodes of a laser cavity are nonorthogonal, the quantum-limited linewidth of the laser is larger by an excess-noise factor than the standard Schawlow-Townes expression. Mode nonorthogonality can exist in the spatial domain, as in unstable-cavity resonators, but also in the polarization domain when the two polarization eigenmodes are nonorthogonal. We show experimentally that these two contributions are independent of each other, i.e., that the excess-noise factor factorizes as a product of the spatial and polarization excess-noise factors.