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141.
142.
The reaction of Cp2*UCl2 with HNSPh2 produces Cp2*UCl2(HNSPh2), which is the first structurally characterized complex of a sulfilimine. The hydrolysis of Cp2*UCl2(HNSPh2) with HNSPh2 · H2O yields a tetrauranium cluster whose heavy atom structure has been determined by x-ray diffraction and which is formulated as a UIV/UV complex: [Cp*(Cl)(HNSPh2)U(μ3-O)(μ2-O)2U(Cl)(HNSPh2)2]2. 相似文献
143.
Henrik Fanø Clausen 《Journal of solid state chemistry》2005,178(11):3342-3351
Two new metal organic framework (MOF) structures have been obtained from the Zn-terephthalic acid (H2BDC)-dimethyl formamide (DMF) system and examined by single-crystal X-ray diffraction: Zn(C8H4O4)(C3H7NO), 1, monoclinic C2/m, a=11.1369(5), b=14.0217(7), , β=106.316(1)°, , , Z=4, R1=0.060, wR2=0.169, S=1.27; Zn(HCO2)3(C2H8N), 2, trigonal , a=8.1818(1), , , , Z=6, R1=0.014, wR2=0.039, S=1.11. Contrary to previously published structures in the same system, the crystals were obtained by solvothermal synthesis at 381 K. Structure 1 consists of 2-D layers stacked in an offset manner to accommodate DMF moieties coordinated to Zn2+ within voids in adjacent layers. Structure 2 consists of a 3-D network constructed from Zn2+ ions bridged by deprotonated formic acid moieties. Over time, the structure of 1 rearranges to Zn(C8H4O4)(C3H7NO)(H2O) [monoclinic P21/n, a=6.6456(2), b=15.2232(5), , β=104.110(2)°, , , Z=4, R1=0.048, wR2=0.100, S=1.07], which is identical to the known MOF-2 structure, obtained by crystallization at ambient conditions. The three structures were determined from crystals with similar crystal habits picked from a single solvothermal synthesis batch. The study demonstrates that MOF syntheses can give not only multiple crystal structures under different conditions, but also that numerous different structures, including some that are metastable, can be formed under identical conditions. 相似文献
144.
M.E. Kletskii A.A. Millov A.V. Metelitsa M.I. Knyazhansky 《Journal of photochemistry and photobiology. A, Chemistry》1997,110(3):857-270
The mechanism of light-induced transformation in the salicylideneaniline molecule was studied by semiempirical PM3 calculations. The structures and energies of the minima and saddle points (transition states) on the S0, S1 and T1 potential energy hypersurfaces (PESs) were obtained, together with the gradient lines on the PESs. The structure-energy scheme was compared with the experimental findings. According to the results obtained, the following principle processes are observed: fast S1 excited state intramolecular proton transfer (ESIPT), followed by typical ESIPT fluorescence; the formation of two S1 twisted intramolecular charge transfer (TICT) structures which quench the ESIPT fluorescence; the diabatic formation of two ground state metastable coloured “post-TICT” structures responsible for photochromism. 相似文献
145.
C. Cismaş I. Grosu G. Plé E. Condamine Y. Ramondenc L. Toupet I. Silaghi-Dumitrescu G. Nemeş A. Terec L. Muntean 《Structural chemistry》2005,16(4):369-377
The synthesis and stereochemistry of some new bis(1,3-oxathian-2-yl) derivatives are reported. The conformational behavior of these compounds and the orientation of their substituents are deduced from the NMR spectra, from the X-ray crystal structures of two compounds and from the ab-initio level calculations. The epimerization of diastereoisomers and the chair ⇌ 22,5-twist equilibria were studied by variable temperature NMR. 相似文献
146.
The geometries of the most stable isomers of gold telluride systems AuTe, Au2Te, and AuTe2 are determined using the MP2 method. The aspect of gold—telluride interaction, the electron correlation, and relativistic
effects on geometry and stability are investigated at the MP2 and CCSD(T) theoretical levels. The results show that the electron
correlation and relativistic effects are responsible not only for gold—gold attraction but also for additional gold—telluride
interaction. The gold—telluride interaction is strong enough to modify the known pattern of bare gold clusters. Both effects
are essential for determining the geometry and relative stability of this type of systems. 相似文献
147.
Based on carbon nanofibers (CNFs) as a solid phase extraction adsorbent, a microcolumn preconcentration method coupled to inductively coupled plasma mass spectrometry (ICP–MS) was developed for the determination of trace elements (Mn, Co and Ni). The effect of various experimental parameters such as pH, sample flow rate and volume, elution solution and interfering ions on the retention of the studied ions have been investigated systematically. During all the steps of the experimental process, Mn, Co and Ni could be quantitatively sorbed on the microcolumn containing CNFs in the range of pH 6.0–9.0, and then eluted completely with 0.5 mol ml− 1 HNO3. A preconcentration factor of 150-fold was obtained. The detection limits for Mn, Co and Ni were 40, 0.4 and 8.0 pg ml− 1, respectively, with relative standard deviations less than 6.0%. In order to validate the proposed method, two certified reference materials of human hair (GBW 07601) and mussel (GBW 08571), and water sample were analyzed with satisfactory results. The recoveries were between 95.0 and 114%. 相似文献
148.
Carbonate Isostructural Anions [SnX3]5? in the Compounds Rb6[SnX3]O0.5 and Cs6[SnX3]O0.5 with X = As, Sb, and Bi The metallic shining compounds Rb6[SnX3]O0.5 and Cs6[SnX3]O0.5 with X = As, Sb, and Bi were prepared from the melt starting from adequate mixtures of the elements and SnO2. They crystallize in the hexagonal system (space group P63/mmc, No. 194, Z = 2) with the lattice constants mentioned in ?Inhaltsübersicht”?. In the structures of the isotypic compounds tin and the main group(V) elements build up trigonal planar anions [SnX3]5? with X = As, Sb, and Bi isostructural to the carbonate anion, oxygen forms isolated O2? ions. The bond lengths Sn? X are significantly shortened with respect to the sums of Pauling covalent radii. The atoms of the units [SnX3]5? are coordinated by alkali metal cations forming trigonal prisms and the O2? anions occupy octahedral holes. 相似文献
149.
New secondary and tertiary amine borane derivatives were prepared in a one-pot reaction starting from primary amine boranes. The reaction involves treatment of an amine borane with 2 equivalents of s-BuLi at −78 °C. In general, mixtures of mono and di metallated products were obtained. Alkyl iodides and benzyl chloride reacted with the lithiated amine, but aldehydes and ketones were reduced. Conversion was high as determined by NMR, but moderate to low yields were obtained after chromatography, possibly due to decomposition on silica. Crystal structures were obtained for the compounds 3a, 3b and 3c. 相似文献
150.
V.A. Ozeryanskii A.F. Pozharskii D.A. Shevchuk A.N. Chekhlov O.A. Dyachenko 《Tetrahedron》2005,61(17):4221-4232
A simple procedure for the synthesis of N,N,N′-trialkyl-1,8-diaminonaphthalenes is described. It consists in partial demethylation (dealkylation) of commercially available proton sponge [1,8-bis(dimethylamino)naphthalene] and some of its derivatives at heating with HBr-KI-DMF system. Limitation, scope and a possible mechanistic pathway for the reaction are discussed. For isomeric 8-dimethylamino-1-methylamino- and 1-dimethylamino-8-methylamino-4-nitronaphthalenes, X-ray measurements have been conducted. The first examples of complete realkylation reactions in the naphthalene proton sponges are reported. 相似文献