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.     

Aminosulf(ox)ides as ligands for Iridium(I)-catalyzed asymmetric transfer hydrogenation

A new class of efficient catalysts was developed for the asymmetric transfer hydrogenation of unsymmetrical ketones. A series of chiral N,S-chelates (6-22) was synthesized to serve as ligands in the iridium(I)-catalyzed reduction of ketones. Both formic acid and 2-propanol proved to be suitable as hydrogen donors. Sulfoxidation of an (R)-cysteine-based aminosulfide provided a diastereomeric ligand family containing a chiral sulfur atom. The two chiral centers of these ligands showed a clear effect of chiral cooperativity. In addition, aminosulfides containing two asymmetric carbon atoms in the backbone were synthesized. Both the sulfoxide-containing beta-amino alcohols and the aminosulfides derived from 1,2-disubstituted amino alcohols gave rise to high reaction rates and moderate to excellent enantioselectivities in the reduction of various ketones. The enantioselective outcome of the reaction was favorably affected by selecting the most appropriate hydrogen donor. Enantioselectivities of up to 97% were reached in the reduction of aryl-alkyl ketones.     

Continuous Time Random Walk with Correlated Waiting Times. The Crucial Role of Inter-Trade Times in Volatility Clustering

In many physical, social, and economic phenomena, we observe changes in a studied quantity only in discrete, irregularly distributed points in time. The stochastic process usually applied to describe this kind of variable is the continuous-time random walk (CTRW). Despite the popularity of these types of stochastic processes and strong empirical motivation, models with a long-term memory within the sequence of time intervals between observations are rare in the physics literature. Here, we fill this gap by introducing a new family of CTRWs. The memory is introduced to the model by assuming that many consecutive time intervals can be the same. Surprisingly, in this process we can observe a slowly decaying nonlinear autocorrelation function without a fat-tailed distribution of time intervals. Our model, applied to high-frequency stock market data, can successfully describe the slope of decay of the nonlinear autocorrelation function of stock market returns. We achieve this result without imposing any dependence between consecutive price changes. This proves the crucial role of inter-event times in the volatility clustering phenomenon observed in all stock markets.     

Effect of hydrogen doping on the magnetic properties of Gd2CuO4

We report the results of ac-susceptibility and dc-magnetization measurements for H_yGd₂CuO₄ (0y0.54). It is shown thatH doping lowers the weak ferromagnetic component in the material. The distinct hysteresis loops observed atT=77 K for both non- and hydrogenated samples change its shape withy. The magnetic ordering temperatures T _N ^Cu and T _N ^Gd , as determined from the temperature dependencies of ac-susceptibility, remain unchanged with sample's hydrogenation. This result seems to indicate that extra electrons are not doped onto the Cu-O planes of Gd₂CuO₄. The frequency dependencies ofx(, T) andx(, T) for bothy=0 andy=0.15 samples are analysed., The maximums ofx andx found at about 200K are considered in terms of susceptibility dependence on the spin-lattice relaxation time (). The anomalies in ac-susceptibility found recently in Gd₂CuO₄ atT _a=8 K andT _b=9.5 K decrease significantly withy. Results are discussed in the context of available data on 214T-type compounds.     

A Robust, Environmentally Benign Catalyst for Highly Selective Hydroformylation

By a sol-gel process a rhodium complex containing a diphosphane with a large natural P-Rh-P bite angle is covalently anchored in a silica matrix (see picture). The immobilized catalyst is a very selective hydroformylation catalyst that is completely and conveniently separated from the product and can be reused in numerous cycles.     

Two successive magnetic transitions in Y2Cu2O5 studied by μSR

Zero field muon spin rotation and magnetic susceptibility experiments on investigation of magnetic properties of cuprateY ₂Cu₂O₅ have been performed in the temperature range 4.2–30 K. Transverse fieldSR-experiments have been also carried out in order to obtain accurate information about transition temperature and to study the influence of the external magnetic field. Our data show that two magnetic phase transitions occur inY ₂Cu₂O₅ with lowering temperature. Upper Neel temperatureT _N=13 K is consistent with previous experimental data. We obtained the temperature dependence of the local magnetic field on the muonB (T) in the antiferromagnetic phase.B (T) reveals a peculiarity (some change of the slope) near the temperatureT _N=7.5 K, which can be interpreted as an additional magnetic phase transition caused by a change in magnetic ordering of the copper subsystem. Applying a small external magnetic field 50 Oe leads to smearing of the peculiarity inB (T) dependence.     

Enhanced susceptibility in LNiO3 perovskites ( L = La,Pr,Nd,Nd0.5Sm0. 5)

The temperature dependence of the resistivity rho(T) and of the dc magnetic susceptibility chi(T) were measured on high-quality LNiO3 (L = La,Pr,Nd,Nd0.5Sm0.5) samples synthesized under high oxygen pressure. Subtraction of the rare-earth contribution to chi(T) allows the presentation of the evolution of the susceptibility of the NiO3 array from Pauli to Curie-Weiss paramagnetism with decreasing bandwidth. A metal-insulator transition occurring at a temperature T(t) = T(N) is first order for L = Pr and Nd; it becomes second order and produces no anomaly in chi(-1)(T) at a T(t)>T(N) for L = Nd0.5Sm0.5. In the antiferromagnetic domain T相似文献   

Magnetic and magnetocaloric properties of Gd1−xScxNi2 solid solutions

Magnetic and heat capacity measurements have been carried out on the polycrystalline Gd_1−xSc_xNi₂ solid solutions (0≤x≤1), which crystallize in the cubic C15 Laves phases superstructure (space group F4?3m). These solid solutions are ferromagnetic with a Curie temperature below 76 K. Their Curie temperature decreases from 75.4 K for GdNi₂ to 13.6 K for Gd_0.2Sc_0.8Ni₂. At high temperatures, all solid solutions, except ScNi₂, are Curie-Weiss paramagnets. The Debye temperature as well as phonon, conduction electron and magnetic contributions to the heat capacity have been determined from heat capacity measurements. The magnetocaloric effect has been estimated both in terms of isothermal magnetic entropy change and adiabatic temperature change for selected solid solutions in magnetic fields up to 3 T.     

Magnetic properties and specific heat of Dy1−xLaxNi2 compounds

Magnetic and specific heat measurements have been carried out on polycrystalline series of single-phase Dy_1−xLa_xNi₂ (0?x?1) solid solutions. The compounds have a Laves-phase superstructure (space group F4¯3m) with the lattice parameter gradually increasing with decreasing Dy content. The samples with x?0.8 are ferromagnetic with the Curie temperature below 22 K. At high temperatures, all solid solutions are Curie-Weiss paramagnets. The Debye temperature, phonon and conduction electron contributions as well as a magnetic contribution to the heat capacity have been determined from specific heat measurements. The magnetocaloric effect was estimated from specific heat measurements performed in a magnetic field of 0.42 and 4.2 T.