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181.
182.
Egle M. Beccalli Prof. Elena Borsini Stefano Brenna Dr. Simona Galli Dr. Micol Rigamonti Gianluigi Broggini Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(5):1670-1678
The isolation of σ‐alkylpalladium Heck intermediates, possible when β‐hydride elimination is inhibited, is a rather rare event. Performing intramolecular Heck reactions on N‐allyl‐2‐halobenzylamines in the presence of [Pd(PPh3)4], we isolated and characterized a series of stable bridged palladacycles containing an iodine or bromine atom on the palladium atom. Indolyl substrates were also tested for isolation of the corresponding complexes. X‐ray crystallographic analysis of one of the indolyl derivatives revealed the presence of a five‐membered palladacycle with the metal center bearing a PPh3 ligand and an iodine atom in a cis position with respect to the nitrogen atom. The stability of the σ‐alkylpalladium complexes is probably a consequence of the strong constraint resulting from the bridged junction that hampers the cisoid conformation essential for β‐hydride elimination. Subsequently, the thus obtained bridged five‐membered palladacycles were proven to be effective precatalysts in Heck reactions as well as in cross‐coupling processes such as Suzuki and Stille reactions. 相似文献
183.
Volodymyr Babizhetskyy Dr. Kurt Hiebl Hansjürgen Mattausch Arndt Simon 《无机化学与普通化学杂志》2010,636(7):1229-1235
New ternary rare earth metal boride carbides with compositions close to RE10B9C10 (RE = Gd, Tb) were prepared from the elements by melting around 1800 K followed by annealing in silica tubes at 1270 K for one month. The crystal structure of the terbium compound was solved by single‐crystal X‐ray diffraction. It crystallizes in a new structure type in the monoclinic space group P21/c, a = 7.937(1), b = 23.786(2), c = 11.172(1) Å, β = 133.74(1)°, Z = 4, R1 = 0.045 (wR2 = 0.11) for 5713 reflections with Io > 2σ(Io). In the structure BC2 units and single carbon atoms are attached to a zigzag boron chain forming the unprecedented B18C18 branching unit with a B–B distance of 2.42(2) Å between these units. In addition isolated carbon atoms occupy the centres of elongated octahedra formed by rare earth metal atoms. Disorder in the terbium position together with anomalous displacement ellipsoids for carbon atoms except of those in the BC2 fragments can be rationalized in terms of a slight deviation in stoichiometry, Tb10B9+xC10–x (x ≈? 0.2). The terbium compound is ferromagnetic below TC ≈? 45 K. Due to the presence of moderately narrow domain walls the magneto‐crystalline energy is small. 相似文献
184.
Cyclization of 1,5-bis(ferrocenylmethylidene)thiocarbonohydrazide with DMAD afforded diastereomeric dimethyl-thiazole-4,5-dicarboxylates. The cis-isomer undergoes ring opening and recyclization to a thiazolone derivative. A further thiazolone was obtained from this precursor with ethyl chloroacetate employing a bifunctional organocatalyst. Due to its propensity to dehydrogenation evidenced by DFT calculations, the studied thiocarbonohydrazide underwent oxidative cyclizations under different conditions to yield a 1,3,4-thiadiazole and a 1,2,4-triazole derivative, respectively. Thermal isomerisation of 1,3,4-thiadiazole into 1,2,4-triazole was also observed. The DMAD-mediated cyclizations of the S-metylated thiocarbonohydrazide and the 1,5-bis(ferrocenylmethylideneamino)guanidine gave 1,2,4-triazole derivatives and a 4-pyrimidone, respectively. The structure of the new compounds was established by IR and NMR spectroscopy, including HMQC, HMBC and DEPT measurements. The solid state structure of a triazole was revealed by single crystal X-ray analysis. 相似文献
185.
Schneider MN Fahrnbauer F Rosenthal T Döblinger M Stiewe C Oeckler O 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(4):1209-1218
The isostructural phases 39R‐Ge0.067Sb0.667Te0.266 (R$\bar 3The isostructural phases 39R-Ge(0.067)Sb(0.667)Te(0.266) (R3m, a=4.2649(1), c=75.061(2) ?) and 39R-Sn(0.067)Sb(0.667)Te(0.266) (R3m, a=4.2959(1), c=75.392(2) ?) were prepared by quenching stoichiometric melts of the pure elements and subsequent annealing at moderate temperatures. Their structures are comparable to "superlattices" synthesized by layer-by-layer deposition onto a substrate. These structures show no stacking disorder by electron microscopy. The structure of the metastable layered phases are similar to that of 39R-Sb(10)Te(3) (equivalent to Sb(0.769)Te(0.231)), which contains four A7 gray-arsenic-type layers of antimony alternating with Sb(2)Te(3) slabs. Joint refinements on single-crystal diffraction data using synchrotron radiation at several K edges were performed to enhance the scattering contrast. These refinements show that the elemental distributions at some atom positions are disordered whereas otherwise the structures are long-range ordered. The variation of the elemental concentration correlates with the variation in interatomic distance. Z-contrast scanning transmission electron microscopy (HAADF-STEM) on 39R-Ge(0.067)Sb(0.667)Te(0.266) confirms the presence of concentration gradients. The carrier-type of the isostructural metal (A7-type lamellae)-semiconductor heterostructures (Ge/Sn-doped Sb(2)Te(3) slabs) varies from n-type (Ge(0.067)Sb(0.667)Te(0.266)) to p-type (Sn(0.067)Sb(0.667)Te(0.266)). Although the absolute values of the Seebeck coefficient reached about 50-70 μV/K and the electrical conductivity is relatively high, the two isotypic phases exhibit a maximal thermoelectric figure of merit (ZT) of 0.06 at 400 °C as their thermal conductivity (κ≈8-9.5 W/mK at 400 °C) lies interestingly in between that of antimony and pure Sb(2)Te(3). 相似文献
186.
A. M. Sheloumov F. M. Dolgushin M. V. Kondrashov P. V. Petrovskii Kh. A. Barbakadze O. I. Lekashvili A. A. Koridze 《Russian Chemical Bulletin》2007,56(9):1757-1764
First ruthenium complexes with a ferrocene-based pincer ligand were synthesized. The cyclometallation of 1,3-bis[(di-tert-butylphosphino)methyl]ferrocene with RuCl2(DMSO)4 in 2-methoxyethanol afforded the RuCl(CO)[{2,5-(But
2PCH2)2C5H2}Fe(C5H5)](RuCl(CO)
) complex (5). Complex 5 reversibly binds CO to form the RuCl(CO)2
complex (6). The analogous reaction in the presence of NaBAr′4 (Ar′ = 3,5-(CF3)2C6H3) produced the cationic complex {Ru(CO)2
}BAr′4 (7). The structures of complexes 5 and 7 were established by single-crystal X-ray diffraction. The X-ray diffraction study revealed an agostic interaction between
one of the C-H bonds of the axial (exo-oriented with respect to the ferrocene iron atom) tert-butyl group and the Ru atom in complexes 5 and 7.
Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1695–1701, September, 2007. 相似文献
187.
Ruslan P. Liferovich 《Journal of solid state chemistry》2004,177(6):2188-2197
Ternary lanthanide scandates (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, and Ho) have been synthesized at ambient pressure. Their structure has been investigated at room temperature by Rietveld analysis of powder X-ray diffraction data. The Ln-scandates are orthorhombic perovskites, adopting space group Pbnm (? 62), a≈b≈√2ap, c≈2ap, Z=4. Heavy lanthanides (Er-Lu), and Y do not form perovskites at ambient conditions. Compositionally driven phase transitions were not observed. The unit-cell parameters decrease with increasing ScO6 octahedron rotation and atomic number of the Ln cation. In common with lanthanide orthoferrites, the uniform structural evolution is interrupted at the middle-heavy part of the lanthanide sequence. This is probably due to an interplay between: (i) enlargement of the ScO6 octahedra relative to BO6 in other perovskites (e.g., FeO6 in GdFeO3); (ii) reduction in size of the first coordination sphere of Ln3+ coincident with the lanthanide contraction; (iii) coincident expansion of the second coordination sphere due to screening effects of OI1 on OI2, and entry of Sc to the lanthanide coordination sphere; (iv) complex mixing between oxygen and lanthanide lanthanide f- and scandium d-orbitals. In the series studied, Ln3+ are in eight-fold coordination (tetragonal antiprism), and are considerably displaced from the center of the LnO8 polyhedron along [001]. Evolution of the crystallochemical characteristics through the Ln orthoscandate series is complex due to both the antipathetic distortions of A- and B-site coordination polyhedra and interaction of the orbitals of oxygen, Ln and Sc. Empirically obtained limits of Goldschmidt and observed viiito tolerance factors for ternary LnBO3 compounds adopting the Pbnm structure are 0.795 and 0.841, respectively. 相似文献
188.
Holger Ott Christoph Matthes Dr. Arne Ringe Dr. Jörg Magull Prof. Dr. Dietmar Stalke Prof. Dr. Uwe Klingebiel Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(18):4602-4609
Borenes and boranes : Silylaminoiminoborenes, such as depicted, were isolated after treatment of halogen triels with silylaminofluoroboranes. In addition, novel aryl‐ and silyl‐substituted diaminofluoroboranes were also prepared in order to substantiate this reaction route.
189.
In this paper, a novel method has been established to determine levodopa with the detection system of potassium ferricyanide‐Fe(III). In the presence of potassium ferricyanide, it has been demonstrated that Fe(III) is reduced to Fe(II) by levodopa at pH 4.0. In addition, the in situ formed Fe(II) reacts with potassium ferricyanide to form soluble prussian blue (KFeIII[FeII(CN)6]). Beer's law is obeyed in the range of levodopa concentrations of 0.01–4.00 μg mL?1 at the maximal absorption wavelength of 735 nm. The linear regression equation is A = 0.0082 + 0.61365 C (μg mL?1) with a correlation coefficient of 0.9996. The detection limit (3σ/k) is 9 ng mL?1, and R.S.D. is 0.73% (n = 11). Moreover, the apparent molar absorption coefficient of indirect determination of levodopa is 1.2 × 105 Lmol?1cm?1. The parameters with regard to determination are optimized, and the reaction mechanism is discussed. This method has been successfully applied to determine levodopa in pharmaceutical, serum and urine samples. Analytical results obtained with this novel assay are satisfactory. 相似文献
190.
配体[C5Me4HR][R=4-BrPh(1),(MeC5H3N)CH2(2)]分别与Mo(CO)6,Ru3(CO)12和Fe(CO)5在二甲苯中加热回流,得到了6个双核配合物trans-[η5-C5Me4R]2Mo2(CO)6(3,4),trans-[(η5-C5Me4R)Ru(CO)(μ-CO)]2(5,6)和trans-[η5-(C5Me4R)Fe(CO)(μ-CO)]2(7,8,).通过元素分析、红外光谱、核磁共振氢谱对配合物的结构进行了表征,并用X-射线单晶衍射法测定了配合物3,5,6和8的结构. 相似文献