Inverse Perovskites (Eu3O)E with E = Sn,In – Preparation,Crystal Structures and Physical Properties

The cubic inverse Perovskites (Eu₃O)In and (Eu₃O)Sn were prepared from the metals and Eu₂O₃ or SnO₂, respectively. For (Eu₃O)In the crystal structure analysis was performed on single crystal X‐ray diffraction data (space group , a = 512.79(3) pm, Z = 1, R_gt(F) = 0.022, wR(F²) = 0.044). The data indicated full occupancy on all sites and a fully ordered structure. According to magnetic susceptibility measurements and X‐ray absorption spectroscopic data at the Eu L_III edge both compounds contain europium in the 4f⁷ (Eu²⁺) electronic state. (Eu₃O)In orders ferromagnetically at 185(5) K, (Eu₃O)Sn shows antiferromagnetic order at 31.4(2) K. Both compounds behave as metallic conductors in electrical resistivity measurements. However, (Eu₃O)In may be classified a metal, while (Eu₃O)Sn is more likely a heavily doped degenerated semiconductor or semimetal according to the absolute values of the resistivity.     

The effect of the solvents on the specific intramolecular C-H...N interactions studied by1H NMR spectroscopy

The analysis of the effect of the solvents on the proton chemical shifts in¹H NMR spectra of 2-vinyloxypyridine indicates that the C—H...N interaction of weak intramolecular hydrogen bond type hinders the formation of intermolecular hydrogen C—H...X and C-H... bonds. The protonating solvents reduce the intramolecular C—H...N interaction due to association with the N atom of the pyridine cycle.Translated fromIzvestiya Akademii Nauk. Seriya Khimieheskaya, No. S, pp. 1202–1204, May, 1996.     

Theoretical studies on the band structures of superconducting solid compounds: Nb3X (X=Si, Ge, Sn, Pb)

The band structures of several analogous superconducting A-15 type solid compounds, Nb3X (X=Si, Ge, Sn, Pb), have been calculated by use of the tight-binding method within the Extended Huckel approximation (EHT). By analysis of their energy bands, densities of states and crystal orbital overlap populations, the dependence of the superconducting transition temperatures (Tc) on the electronic structures and bondings is qualitatively elucidated.     

Cleavage of the Fe—Fe Bond of （Me2SiSiMe2） [η^5－C5H4Fe（CO）2]2 with Na／Hg and Molecular Structure of the Ring－Opened Complex

The reaction of the rifle cyclic complex (1) with sodium amalgam in THF resulted in the expected cleavage of the Fe-Fe bond to afford his-sodium salt ( Me2SiSiMe2 ) [η^5-C5H4Fe(CO)2]2 (4). The latter was not isolated and was used directly to react with MeI, PhCH2Cl, CH3C(O)Cl, PhC(O)Cl,Cy3SnCl (Cy= cyclohexyl) or Ph3SnCl to afford corresponding ring-opened derivatives (Me2SiSiMe2) [η^5-C5H4Fe(CO)2]2 [5, R=Me; 6, R=PhCH2; 7, R=CH3C(O); 8, R=PhC(O); 9, R = Cy3Sn or 10, R = Ph3Sn ]. The crystal and molecular structures of 10 were determined by X-ray diffraction analysis. The molecule took the desired ant/ conformation around the Si-Si bond. The length of the Si--Si bond is 0.2343(3)nm, which is essentially identical to that in the cyclic structure of 1[0.2346(4) tun]. This result unambiguously demonstrates that the Si--Si bond in the cyclic structure of 1 is not subject to obvious strain.     

Monte Carlo simulation of spatial distribution of X rays in multifilm targets. III: optimum design as applied to W/Al‐film targets

The brightness of the X‐ray source in a W/Al‐film target used for X‐ray projection microscopy was studied by an approach using the Monte Carlo simulation. Since continuous X rays generated in a thin film have a specific angular distribution of emission, the brightness of the continuous X‐ray source cannot simply be estimated on the assumption that the angular distribution is homogeneous. The newly developed approach using the Monte Carlo simulation enables the evaluation of the effective source size, angular distribution, and brightness of a continuous X‐ray source with sufficient accuracy that it leads to the optimum design of a high‐brightness X‐ray source for uses such as X‐ray projection microscopy. The Monte Carlo calculations were performed for W(Δz)/Al (200 µm)‐film targets with different thicknesses of W film, Δz, under bombardment of 60 kV electrons. The results have suggested an optimum design consisting of a W (2 µm)/Al (200 µm)‐film target as most promising for providing an X‐ray source of higher brightness than the W (5 µm)/Al (200 µm)‐film target, which has already been in practice for X‐ray projection microscopy. Copyright © 2006 John Wiley & Sons, Ltd.     

Alkali Metal Compounds of Hydroquinone: Synthesis and Crystal Structure

A number of novel routes to the alkali metal compounds of hydroquinone M₂[p‐C₆H₄O₂] (M = Li, Na, K, Rb, Cs) and M[p‐C₆H₄O(OH)] (M = K, Rb, Cs) have been synthetically explored. The selective synthesis of the alkali 4‐hydroxyphenolates and 1, 4‐phenylenediolates is based on optimized reaction conditions (solvents, temperatures). All compounds were structurally characterized by means of powder X‐ray diffraction using Rietveld profile refinement including C—C and C—O bond distance restraints. The atomic arrangement of M₂[p‐C₆H₄O₂](M = Na, K) (tetragonal, space group: P4₂/ncm) is characterized by infinite pillars of [M₂^[3]O₂^[3]]‐units along the c axis connected by [p‐C₆H₄O₂]^2—‐anions with stacking direction along c. The coordinatively unsaturated alkali metals, surrounded by three oxygen atoms, exhibit symmetrical (K) as well as asymmetrical (Na) interactions with the phenylene rings. M[p‐C₆H₄O(OH] (M = K, Rb) (tetragonal, space group: P4/n) forms hydrogen‐bridged linear chains of [p‐C₆H₄O(OH)]^—‐anions along the c direction. The phenylene planes of neighboring chains have an almost orthogonal arrangement while the interchain planes are parallel. K and Rb are fourfold coordinated by two different oxygen coordination spheres.     

Bis(dimethylamino)trifluoromethylsulfonium Salze: [CF3S(NMe2)2]+[Me3SiF2]‐, [CF3S(NMe2)2]+[HF2]‐ und [CF3S(NMe2)2]+[CF3S]‐

Bis(dimethylamino)trifluoro sulfonium Salts: [CF₃S(NMe₂)₂]⁺[Me₃SiF₂]^‐, [CF₃S(NMe₂)₂]⁺ [HF₂]^‐ and [CF₃S(NMe₂)₂]⁺[CF₃S]^‐ From the reaction of CF₃SF₃ with an excess of Me₂NSiMe₃ [CF₃(NMe₂)₂]⁺[Me₃SiF₂]^‐ (CF₃‐BAS‐fluoride) ( 5 ), from CF₃SF₃/CF₃SSCF₃ and Me₂NSiMe₃ [CF₃S(NMe₂)₂]⁺‐ [CF₃S]^‐ ( 7 ) are isolated. Thermal decomposition of 5 gives [CF₃S(NMe₂)₂]⁺ [HF₂]^‐ ( 6 ). Reaction pathways are discussed, the structures of 5 ‐ 7 are reported.     

The Structure of Bis[N‐6‐aminopyridyl‐N‐(1S)‐(+)‐10‐camphorsulfonylamino]palladium in the Solid State and in Solution

The complex, bis[N‐6‐aminopyridyl‐N‐(1S)‐(+)‐10‐camphorsulfonylamino]palladium, Pd[(S)‐APCS]₂, 1 , was prepared by reaction of 2‐[(1S)‐(+)‐10‐camphorsulfonamino]‐6‐aminopyridine with PdCl₂ in THF. Complex 1 has been characterized by spectroscopic methods and its structure has been determined by X‐ray crystallography. Crystal data: space group C2, a= 16.082 (2), b = 17.104 (2), c = 13.051 (2)Å, β = 99.95 (1)°, V = 3535.9 (8) ų, Z = 2 with final residuals R1 = 0.0491 and wR2 = 0.0944. Two independent molecules, (S,S)‐Pd[(S)‐APCS]2, 1a , and (R,R)‐Pd[(S)‐APCS]2, 1b , were found in each asymmetric unit, which exchange to each other via a series of nitrogen inversion and C‐C bond rotation. The inversion energy (ΔGc₁^≠) and the energy barrier (δGc₂^≠) were 11.5 ± 0.1 Kcal mol^?1 at 246 K and 9.8 ± 0.1 Kcal mol^?1 at 199 K, respectively, calculated by dynamic NMR data.     

Stereoselective and Enantioselective Syntheses of the Four Stereoisomers of Muscol from (3RS)‐Muscone

Two trans stereoisomers of 3‐methylcyclopentadecanol (=muscol), (1R,3R)‐ 2 and (1S,3S)‐ 2 , were efficiently synthesized from (3RS)‐3‐methylcyclopentadecanone (=muscone; (3RS)‐ 1 ) by a highly stereoselective reduction (Scheme). L‐Selectride^® (=lithium tri(sec‐butyl)borohydride) was used, followed by the enantiomer resolution by lipase QLG (Alcaligenes sp.). The cis stereoisomers of muscol, (1S,3R)‐ 2 and (1R,3S)‐ 2 , were obtained by the Mitsunobu inversion of (1R,3R)‐ 2 and (1S,3S)‐ 2 , respectively (Scheme). The absolute configuration of (1R,3R)‐ 2 was determined by X‐ray crystal‐structure analysis of its 3‐nitrophthalic acid monoester, 2‐[(1R,3R)‐3‐methylcyclopentadecyl hydrogen benzene‐1,2‐dicarboxylate ((1R,3R)‐ 3b ), and by oxidation of (1R,3R)‐ 2 to (3R)‐muscone.     

Reactions of α,β‐Unsaturated Thioamides with Diazo Compounds

Several reactions of the α,β‐unsaturated thioamide 8 with diazo compounds 1a – 1d were investigated. The reactions with CH₂N₂ ( 1a ), diazocyclohexane ( 1b ), and phenyldiazomethane ( 1c ) proceeded via a 1,3‐dipolar cycloaddition of the diazo dipole at the C?C bond to give the corresponding 4,5‐dihydro‐1H‐pyrazole‐3‐carbothioamides 12a – 12c , i.e., the regioisomer which arose from the bond formation between the N‐terminus of the diazo compound and the C(α)‐atom of 8 . In the reaction of 1a with 8 , the initially formed cycloadduct, the 4,5‐dihydro‐3H‐pyrazole‐3‐carbothioamide 11a , was obtained after a short reaction time. In the case of 1c , two tautomers 12c and 12c ′ were formed, which, by derivatization with 2‐chlorobenzoyl chloride 14 , led to the crystalline products 15 and 15 ′. Their structures were established by X‐ray crystallography. From the reaction of 8 and ethyl diazoacetate ( 1d ), the opposite regioisomer 13 was formed. The monosubstituted thioamide 16 reacted with 1a to give the unstable 4,5‐dihydro‐1H‐pyrazole‐3‐carbothioamide 17 .