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31.
Part of molybdenum introduced in SnO2 by various methods is found to be stabilized in the pentavalent state at substitutional positions. The ESR spectra of Mo5+ ions are characterized by the following parameters: gxx = 1.891; gyy = 1.835 and gzz = 1.923, Axx = 24 G, Ayy = 30 G and Azz = 70 G. There are, in addition, two sets of superhyperfine structures due to the two tins located along the crystallographic c axis (290 G) and to the four tins lying in a diagonal plane of the unit cell containing four oxygens (51 G), consistent with a 3dx2-y2 + λ 3dz2 ground state. The variations of the Mo5+ ESR spectrum upon heating the samples in various atmospheres (O2, H2) suggest that molybdenum enters the SnO2 lattice also as Mo4+. 相似文献
32.
A class of extended 2,5‐disubstituted‐1,3,4‐oxadiazoles R1‐C6H4‐{OC2N2}‐C6H4‐R2 (R1=R2=C10H21O 1 a , p‐C10H21O‐C6H4‐C?C 3 a , p‐CH3O‐C6H4‐C?C 3 b ; R1=C10H21O, R2=CH3O 1 b , (CH3)2N 1 c ; F 1 d ; R1=C10H21O‐C6H4‐C?C, R2=C10H21O 2 a , CH3O 2 b , (CH3)2N 2 c , F 2 d ) were prepared, and their liquid‐crystalline properties were examined. In CH2Cl2 solution, these compounds displayed a room‐temperature emission with λmax at 340–471 nm and quantum yields of 0.73–0.97. Compounds 1 d , 2 a – 2 d , and 3 a exhibited various thermotropic mesophases (monotropic, enantiotropic nematic/smectic), which were examined by polarized‐light optical microscopy and differential scanning calorimetry. Structure determination by a direct‐space approach using simulated annealing or parallel tempering of the powder X‐ray diffraction data revealed distinctive crystal‐packing arrangements for mesogenic molecules 2 b and 3 a , leading to different nematic mesophase behavior, with 2 b being monotropic and 3 a enantiotropic in the narrow temperature range of 200–210 °C. The structural transitions associated with these crystalline solids and their mesophases were studied by variable‐temperature X‐ray diffractometry. Nondestructive phase transitions (crystal‐to‐crystal, crystal‐to‐mesophase, mesophase‐to‐liquid) were observed in the diffractograms of 1 b, 1 d , 2 b, 2 d , and 3 a measured at 25–200 °C. Powder X‐ray diffraction and small‐angle X‐ray scattering data revealed that the structure of the annealed solid residue 2 b reverted to its original crystal/molecular packing when the isotropic liquid was cooled to room temperature. Structure–property relationships within these mesomorphic solids are discussed in the context of their molecular structures and intermolecular interactions. 相似文献
33.
Ruthenium porphyrins [Ru(F(20)-TPP)(CO)] (F(20)-TPP = 5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato dianion) and [Ru(Por*)(CO)] (Por = 5,10,15,20-tetrakis[(1S,4R,5R,8S)-1,2,3,4,5,6,7,8-octahydro-1,4:5,8-dimethanoanthracen-9-yl]porphyrinato dianion) catalyzed intramolecular amidation of sulfamate esters p-X-C(6)H(4)(CH(2))(2)OSO(2)NH(2) (X = Cl, Me, MeO), XC(6)H(4)(CH(2))(3)OSO(2)NH(2) (X = p-F, p-MeO, m-MeO), and Ar(CH(2))(2)OSO(2)NH(2) (Ar = naphthalen-1-yl, naphthalen-2-yl) with PhI(OAc)(2) to afford the corresponding cyclic sulfamidates in up to 89% yield with up to 100% substrate conversion; up to 88% ee was attained in the asymmetric intramolecular amidation catalyzed by [Ru(Por)(CO)]. Reaction of [Ru(F(20)-TPP)(CO)] with PhI[double bond]NSO(2)OCH(2)CCl(3) (prepared by treating the sulfamate ester Cl(3)CCH(2)OSO(2)NH(2) with PhI(OAc)(2)) afforded a bis(imido)ruthenium(VI) porphyrin, [Ru(VI)(F(20)-TPP)(NSO(2)OCH(2)CCl(3))(2)], in 60% yield. A mechanism involving reactive imido ruthenium porphyrin intermediate was proposed for the ruthenium porphyrin-catalyzed intramolecular amidation of sulfamate esters. Complex [Ru(F(20)-TPP)(CO)] is an active catalyst for intramolecular aziridination of unsaturated sulfonamides with PhI(OAc)(2), producing corresponding bicyclic aziridines in up to 87% yield with up to 100% substrate conversion and high turnover (up to 2014). 相似文献
34.
[reaction: see text] Unsaturated sulfonamides underwent direct intramolecular aziridination catalyzed by Rh(2)(OAc)(4) with PhI(OAc)(2) and Al(2)O(3) to give the corresponding aziridine products in excellent yields (up to 98%) and with good to excellent conversions. High turnovers (up to 1375) were achieved. The intermolecular rhodium-catalyzed amidation of cholesteryl acetate with PhI=NTs or PhI(OAc)(2)/NH(2)R as the nitrogen source exhibited both excellent regio- and alpha-selectivity (alpha/beta ratio up to 9:1). 相似文献
35.
36.
Chun‐Bo Liu Guang‐Bo Che Chuan‐Bi Li Yun‐Cheng Cui 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(4):m153-m155
An in situ reaction under hydrothermal conditions leads to the formation of the title compound, diaqua(pyridine‐2‐carboxylato)(pyridine‐2,6‐dicarboxylato)indium(II) trihydrate, [In(C6H4NO2)(C7H3NO4)(H2O)2]·3H2O, in which the central InIII atom is seven‐coordinated by one pyridine‐2,6‐dicarboxylate ligand, one pyridine‐2‐carboxylate ligand and two water molecules in a pentagonal–bipyramidal coordination environment. An indium(III)–water chain based on an unusual water pentamer is observed. 相似文献
37.
Négrier F Marceau E Che M Giraudon JM Gengembre L Löfberg A 《The journal of physical chemistry. B》2005,109(7):2836-2845
1.5 Ni wt %/Al2O3 catalysts have been prepared by incipient wetness impregnation using [Ni(diamine)x(H2O)(6-2x)]Y2 precursors (diamine = 1,2-ethanediamine (en) and trans-1,2-cyclohexanediamine (tc); x = 0, 1, and 2; Y = NO3- and Cl-), to avoid the formation, during calcination, of difficult-to-reduce nickel aluminate. N2 was chosen for thermal treatment to help reveal and take advantage of the reactions occurring between Ni2+, ligands, counterions, and support. In the case of [Ni(en)2(H2O)2]Y2 salts used as precursors, in situ UV-vis and DRIFT spectroscopies show that after treatment at 230 degrees C Ni(II) ions are grafted to alumina via two OAl bonds and that the diamine ligands still remain coordinated to grafted nickel ions but in a monodentate way, bridging the cation with the alumina surface. With Y = Cl-, the chloride counterions desorb as hydrogen chloride, and hydrogen released upon decomposition of the en ligands is able to reduce a fraction of nickel ions into metal as evidenced by XPS. In contrast, with Y = NO3-, compounds such as CO or NO are formed during thermal treatment, indicating that nitrate ions burn the en ligands. After thermal treatment at 500 degrees C, a surface phase containing Ni(II) ions forms, characterized by XPS and UV-vis spectroscopy. Temperature-programmed reduction shows that these ions can be quantitatively reduced to the metallic state at 500 degrees C, in contrast with the aluminate obtained when the preparation is carried out from [Ni(H2O)6]2+, which is reduced only partly at 950 degrees C. On the other hand, a total self-reduction of nickel complexes leading to 2-5-nm metal particles is obtained upon thermal treatment via the hydrogen released by a hydrogen-rich ligand such as tc, whatever the Y counterion. An appropriate choice of the ligand and the counterion allows then to obtain selectively Ni(II) ions or a dispersed reduced nickel phase after treatment in N2, as a result of the reactions occurring between the chemical partners present on alumina. 相似文献
38.
A new anthraquinone glycoside, rubiayannone‐A ( 1 ), and a new coumarin, rubilatin‐A ( 2 ), together with twenty‐two known compounds were isolated and characterized from the roots of Rubia ustulata. A new anthraquinone, 2‐carbomethoxyanthraquinone ( 3 ), and rubiayannone‐A, 2‐formylanthraquinone were obtained from the roots of R. yunnanensis. The structures of those compounds were elucidated by spectroscopic methods. The antiplatelet aggregation activity of the isolated compounds 1, 4~6 were also discussed. 相似文献
39.
Che S Lim S Kaneda M Yoshitake H Terasaki O Tatsumi T 《Journal of the American Chemical Society》2002,124(47):13962-13963
The presence of various counteranions at the interfacial region of the silicate-surfactant mesophase introduces opportunities for manipulation of the phase structure. Well-ordered 3D-hexagonal P63/mmc, cubic Pmn, 2D-hexagonal p6mm, and cubic Iad mesoporous materials have been synthesized with the same surfactant, cetyltriethylammonium bromide, in the presence of various acids. The counteranions of acidic media have resulted in increasing the surfactant packing parameter g in the order SO42- < Cl- < Br- < NO3-, which leads to the different time course of formation of mesostructures. The effect of counteranions on the formation of mesostructures is explained in terms of not only the adsorption strength on the headgroups of the surfactant micelle but also the rate of silica condensation affecting the charge density matching between the surfactant and silica. It has been found that the mesophase is always transformed from the larger g parameter into the smaller one. The distinct morphologies of the 3D-hexagonal P63/mmc mesophases have been rationally explained by supposing this particular mesostructure. The cubic Iad phase has been first synthesized under acidic conditions. 相似文献
40.