Magnetic order in LaEuSrCuO studied [2pt] by Fe Mössbauer spectroscopy

⁵⁷Fe M?ssbauer effect studies of La_1.65Eu_0.20Sr_0.15CuO₄ doped with 0.5 at% ⁵⁷Fe performed in the temperature region 300 K > T > 4.2 K give an onset temperature for magnetic ordering of K. This temperature practically is the same as that found in Nd doped La_2-xSr_xCuO₄. It indicates that the magnetic ordering temperature in the LTT phase of rare earth (RE) doped La_2-xSr_xCuO₄ is independent of the RE moment. The direction of the ⁵⁷Fe magnetic moment in the magnetically ordered state is within the CuO₂ plane, while it has been found to be parallel to the c-axis in Nd doped La_2-xSr_xCuO₄. Received: 23 June 1998 / Accepted: 14 July 1998     

Acylation of α-(N-carbamoyl)alkylcuprates and alkyl- or aryl(halo)cuprates

α-(N-Carbamoyl)alkylcuprates [R₂CuLi·LiX or RCuXLi (X=CN, Cl)] when prepared from THF soluble CuX·2LiCl (X=Cl, CN) undergo a reliable and generally high yield reaction with aroyl, alkanoyl, and alkenoyl chlorides to provide a rapid and efficient synthesis of α-carbamoyl ketones. Cuprates prepared from acyclic, cyclic, and a functionalized carbamate can be utilized. Although yields are a function of cuprate reagent and substrate structure, nearly quantitative yields can be obtained with reagents generated from 2RLi+CuCN·2LiCl. The use of reagents generated from CuCl·2LiCl are more efficient in the α-(N-carbamoyl)alkyl ligand, although yields are slightly lower. Acylation of alkyl(chloro)cuprates generated from one equivalent of CuCl·2LiCl and organolithium or Grignard reagents provides an efficient and high yield procedure for ketone synthesis.     

Growth of large La2−xSrxCuO4 single crystals using tilting-mirror-type infrared heating image furnace

Large single crystals of La_2−xSr_xCuO₄ (LSCO) high-T_c superconductors were grown by the infrared heating floating zone (IR-FZ) method using a tilting-mirror-type image furnace. The maximum diameter of the LSCO crystals increased to 10 mm in the tilting-mirror-type image furnace from 6 mm in the conventional image furnace. CuO rich feeds were required for the crystal growth using the tilting-mirror-type image furnace to compensate for the lack of CuO caused by the significant evaporation of CuO during the growth. The evaporation of CuO was affected by the tilting angle of the mirrors of the image furnace and by feed diameter. The optimized growth conditions were as follows: mirror tilting angle, 20°; feed diameter, 10 mm∅; and feed composition 50.7 mol% CuO.     

Two Unusual Carbohydrate Reactions: Nucleophilic Ring Opening of an Anhydrosugar and Reductive Elimination with Co‐occurring Hydrogenation

Treatment of the 1,6‐anhydrosugar epoxide 5 with a cyano‐Gilman cuprate [(CuCN (6 eq.), MeLi (12 eq.)] surprisingly led to the open chain rearranged (2S,3R)‐1,2‐dihydroxy‐3,6‐dimethylheptan‐4‐one (7), structurally confirmed by conversion to the corresponding diacetate 8. Another unusual reaction was found by hydrogenation of the 2‐tosyl‐1‐bromosugar 11, leading in one operation to the twofold deoxygenated chiral pyran derivative 14. This procedure might prove to be useful in the rapid deoxygenation of sugar derivatives.     

Heterobimetallic Cuprates Consisting of a Redox‐Switchable,Silicon‐Based Metalloligand: Synthesis,Structures, and Electronic Properties

A series of bimetallic silyl halido cuprates consisting of the new tripodal silicon‐based metalloligand [κ³N‐Si(3,5‐Me₂pz)₃Mo(CO)₃]^? is presented (pz=pyrazolyl). This metalloligand is straightforwardly accessible by reacting the ambidentate ligand tris(3,5‐dimethylpyrazolyl)silanide ({Si(3,5‐Me₂pz)₃}^?) with [Mo(CO)₃(η⁶‐toluene)]. The compound features a fac‐coordinated tripodal chelating ligand and an outward pointing, “free” pyramidal silyl donor, which is easily accessible for a secondary coordination to other metal centers. Several bimetallic silyl halido cuprates of the general formula [CuX{μ‐κ¹Si:κ³N‐Si(3,5‐Me₂pz)₃Mo(CO)₃}]^? (X=Cl, Br, I) have been synthesized. The electronic and structural properties of these complexes were probed in detail by X‐ray diffraction analysis, electrospray mass spectrometry, infrared‐induced multiphoton dissociation studies, cyclic voltammetry, spectroelectrochemistry, gas‐phase photoelectron spectroscopy, as well as UV/Vis and fluorescence spectroscopy. The heterobimetallic complexes contain linear two‐coordinate copper(I) entities with the shortest silicon–copper distances reported so far. Oxidation of the anionic complexes in methylene chloride and acetonitrile solutions at ${E{{0\hfill \atop 1/2\hfill}}}$ =?0.60 and ?0.44 V (vs. ferrocene/ferrocenium (Fc/Fc⁺)), respectively, shows substantial reversibility. Based on various results obtained from different characterization methods, as well as density functional theory calculations, these oxidation events were attributed to the Mo⁰/Mo^I redox couple.     

New Ideas for Understanding the Structure and Magnetism in AgF2: Prediction of Ferroelasticity

In the search for new high-temperature superconductors, it has been proposed that there are strong similarities between the fluoroargentate AgF₂ and the cuprate La₂CuO₄. We explored the origin of the possible layered structure of AgF₂ by studying its parent high-symmetry phase and comparing these results with those of a seemingly analogous cuprate, CuF₂. Our findings first stress the large differences between CuF₂ and AgF₂. Indeed, the parent structure of AgF₂ is found to be cubic, naturally devoid of any layering, even though Ag²⁺ ions occupy trigonal sites that, nevertheless, allow the existence of a Jahn-Teller effect. The observed Pbca orthorhombic phase is found when the system is cooperatively distorted by a local E⊗e trigonal Jahn-Teller effect around the silver sites that creates both geometrical and magnetic layering. While the distortion implies that two Ag²⁺−F⁻ bonds increase their distance by 15 % and become softer, our simulations indicate that covalent bonding and interlayer electron hopping is strong, unlike the situation in cuprate superconductors, and that, in fact, exfoliation of individual planes might be a harder task than previously suggested. As a salient feature, these results prove that the actual magnetic structure in AgF₂ is a direct consequence of vibronic contributions involved in the Jahn-Teller effect. Finally, our findings show that, due to the multiple minima intrinsic to the Jahn-Teller energy surface, the system is ferroelastic, a property that is strongly coupled to magnetism in this argentate.     

Highly enantioselective conjugate addition of AlMe3 to linear aliphatic enones by a designed catalyst

2-Hydroxy-2'-alkylthio-1,1'-binaphthyl compounds are catalytic promoters of the 1,4-addition of AlMe(3) to linear aliphatic enones in THF at -40 to -48 degrees C in the presence of [Cu(MeCN)(4)]BF(4). At ligand loadings of 5-20 mol %, enantioselectivities of 80-93 % are realised for most substrates. To attain these values, the use of highly pure AlMe(3) is mandatory. The presence of methylalumoxane (MAO), derived by hydrolysis, leads to reduced enantioselectivity and a conjugate addition product.     

Electrodynamics of the vortex lattice in untwinned YBaCuO by complex impedance measurements

We report complex impedance measurements in an untwinned YBaCuO crystal. Our broad frequency range covers both the quasi static response and the resistive response of the vortex lattice. It allow us to characterize the irreversibility line without the need of any frequency dependent pinning parameters. We confirm the validity of the two modes model of vortex dynamic, and extract both the surface critical current and the flux flow resistivity around the first order transition T_m. This latter is identified by the abrupt loss of pinning and by an unexpected step of (T) at T_m. Received 22 November 2002 / Received in final form 17 February 2003 Published online 20 June 2003 RID="a" ID="a"e-mail: alain.pautrat@ismra.fr RID="b" ID="b"UMR 6508 associée au CNRS