Enantioselective Evans-Tishchenko reduction of β-hydroxyketone catalyzed by lithium binaphtholate

Lithium diphenylbinaphtholate catalyzed the enantioselective Evans-Tishchenko reduction of achiral β-hydroxyketones to afford monoacyl-protected 1,3-diols with high stereoselectivities. In the reaction of racemic β-hydroxyketones, kinetic optical resolution occurred in a highly stereoselective manner.     

Synthesis and Properties of New Laser Dyes Containing 4-(2-Thienyl)Pyridine Skeleton

Abstract

Three 4-(oligothienyl)pyridines and four α,ω-di(4-pyridyl)oligo-thiophenes were prepared and the effect of conjugated thiophene rings on their fluorescence properties were examined. 4-(2,2′-Bithienyl-5-yl)pyridine and 2,5-di(4-pyridyl)thiophene exhibited laser dye emission upon pumping with a nitrogen laser and the conversion efficiency of the latter was 1.5 times as great as that of a commercial laser dye PBBO at 400 nm.     

Doping effect on the carrier scattering in iron-pnictide superconductors studied by charge transport

In order to reveal the role of “carrier doping” in the iron-based superconductors, we investigated the transport properties of the oxygen-deficient iron-arsenides LnFeAsO_1−y (Ln=La, Ce, Pr and Nd) over a wide doping range. We found that the effect of “doping” in this system is mainly on the carrier scattering rather than carrier density, quite distinct from that in high-T_c cuprates. In the case of La system with lower T_c, the low temperature resistivity is dominated by T² term and fairly large magnetoresistance is observed. On the other hand, in the Nd system with higher T_c, carriers are subject to stronger scattering showing nearly T-linear resistivity and small magnetoresistance. Such strong scattering appears intimately correlated with high-T_c superconductivity in the iron-based system.     

Complete Fermi surface in BaFe2As2 observed via Shubnikov-de Haas oscillation measurements on detwinned single crystals

We show that the Fermi surface (FS) in the antiferromagnetic phase of BaFe(2)As(2) is composed of one hole and two electron pockets, all of which are three dimensional and closed, in sharp contrast to the FS observed by angle-resolved photoemission spectroscopy. Considerations on the carrier compensation and Sommerfeld coefficient rule out existence of unobserved FS pockets of significant sizes. A standard band structure calculation reasonably accounts for the observed FS, despite the overestimated ordered moment. The mass enhancement, the ratio of the effective mass to the band mass, is 2-3.     

Singlet Excitation Energy Migration in the Glassy and Single Crystalline States of 1,3-Diphenyl-5-(p-chlorophenyl)-2-pyrazoline

The crystal and molecular structure of the title compound were determined: a = 14.375(3), b = 11.534(3), c = 7.972(2) Å, α = 71.694(5), β = 79.125(5), γ - 74.861(5)°; space group PI. Refinement including all of the observed reflections (3145) leads to R = 0.086 (R_w= 0.074).

The molecular form in the crystalline state is fully extended in agreement with the suggestion by Birner et al. (Mol. Cryst. Liq. Cryst., 80, 11 (1982)), based on a NDDO-semiempirical calculation.

Whereas for the molecular form in the nematic liquid crystalline state a slightly parallel arrangement (～ 60°) of the dipole moment components perpendicular to the long axis is proposed, in the crystalline state these components are at an angle ～ 120° to each other, and somewhat antiparallel.

Preceding the melting point by approximately 10 degrees, DSC and thermal microscopy signals were observed; these depend eventually on solid-state polymorphism.     

Gold and Silver Chains Supported by Linear Hexaphosphine Ligands

A new linear hexaphosphine, rac‐cis,cis,trans‐ bis{[(diphenylphosphinomethyl)phenylphosphinomethyl]phenylphosphino}methane ( P₆ ), was synthesized and isolated as a pure isomer, confirmed by transforming to the corresponding phosphine sulfide. The methylene‐bridged linear hexaphosphine readily organized flexible gold(I) and silver(I) hexanuclear chains, [M₆(μ‐ P₆ )₂]X₆ (X₆=(OTf)₆, M=Au ( 1 ), Ag ( 2 ); X₆=Cl₂(PF₆)₄, M=Au ( 3 )). The hexaphosphine also supported a tetrasilver(I) complex [Ag₄(μ‐ P₆ )₂](OTf)₄ ( 4 ), which was readily transformed by treatment with AgOTf into 3 , revealing a drastic alternation of the two P₆ arrangement. The hexagold(I) chains exhibited a considerably red‐shifted absorption (～410 nm) and emission (540–580 nm) to ¹[5d_σ*→6p_σ] and from ³[5d_σ*→6p_σ] excited states of the metal centers, respectively. The new linear hexaphosphine could be a useful tool to construct linear metal clusters as subnano building blocks.