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.     

Curie temperature of Ni−Fe alloys in the region (24÷35)% Ni from Mössbauer experiments

Summary The ferromagnetic-transition temperatureT _c of carefully homogeneized Ni−Fe alloys has been determined by means of M?ssbauer transmission experiments down to liquid-nitrogen temperature, for Ni contents ranging between 24% and 35% (atomic). The results show thatT _c decreases rapidly with decreasing Ni concentration, according to a nonlinear behaviour different from the linear one usually observed in other Ni alloys. The present data agree with the ones of other authors, but differ from other data probably obtained in less homogeneized samples.

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Riassunto La temperatura di transizione ferromagneticaT _c di leghe Fe−Ni preparate in laboratorio con cura particolare per garantire l'omogeneità è stata misurata mediante misure M?ssbauer fino alla temperatura dell'azoto liquido per concentrazioni di Ni variabili tra 24 e 35% (atomico). I risultati mostrano cheT _c è una funzione rapidamente decrescente al diminuire della concentrazione di Ni con un andamento non lineare caratteristico di tali leghe e diverso da quello lineare osservato su altre leghe di Ni. I dati ottenuti sono in accordo con quelli di altri autori, ma differiscono da altri risultati probabilmente ottenuti su campioni non sufficientemente omogenei.

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Реэюме Проводится иэмерение температуры ферромагнитного переходаT _c в сплавах Ni−Fe с контролируемой однородностъю. Иэмерения проводятся с помощъю мессбауэровских экспериментов при температурах вплоть до температуры жидкого азота и для концентраций никеля в области от 24 до 35 атомных процентов. Полученные результаты показывают, чтоT _c уменьшается быстро с уменьшением концентрации Ni, согласно нелинейному поведению, которое отлично от линейного поведения, обычно наблюдаемого в других сплавах никеля. Полученные данные согласуются с даннымн других авторов, но отличаются от других данных, которые, вероятно, получены на менее однородных образцах.

     

Applied research on amorphous magnetic materials

Amorphous magnetic materials are increasingly becoming an industrial reality, with a variety of applications to electronics and electrical engineering. Many research lines are in progress for what concerns the production techniques, the understanding of the structure and properties of amorphous ribbons, the optimization and extension of their applications. The fast quenching methods used to obtain amorphous materials will first be reviewed, also describing an experimental apparatus set up by the authors for laboratory investigations of rapid solidification processes. Becauses of the non equilibrium structure of amorphous metallic alloys, various relaxation effects are expected to occur, which may partially limit the use of these materials. Studies of these relaxation phenomena, performed by different methods, including Mossbauer spectroscopy will also be reviewed, showing their importance in better understanding the amorphous structure. Finally much attention will be devoted to actual applications of amorphous magnetic materials. Emphasis will be placed on the prospective applications of amorphous ribbons characterized by very low power losses to magnetic cores of distribution transformers, pointing to the possible advantages, but also to the technical problems involved with the substitution of crystalline laminations with the new amorphous materials.     

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.     

Torque magnetometer measurements of the temperature dependence of induced anisotropy energy and of saturation magnetization in amorphous Fe40Ni40P14B6

Induced anisotropy energy K_u and saturation magnetization M have been measured as a function of temperature T between 77 K and T_c on co$\text{n}$venient specimens of amorphous Fe₄₀Ni₄₀P₁₄B₆ by means of a torque magnetometer. The M vs. T curve is found to follow an anomalously low behaviour with respect to crystalline materials. The exper$\text{i}$mental K_u vs. T curve is well fitted by a M² law, also different from higher power laws typical of crystalline alloys.