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71.
Maria Ana Castro Zulema D. Chaia Oscar E. Piro Fabio D. Cukiernik Eduardo E. Castellano Marcia Rusjan 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(7):m393-m395
The title compound, tetrakis(μ‐3,4,5‐triethoxybenzoato‐κ2O:O′)bis[(pyrazine‐κN)rhodium(II)](Rh—Rh), [Rh2(C13H17O5)4(C4H4N2)2], crystallizes on an inversion centre in the triclinic space group . The equatorial carboxylate ligands bridge the two RhII atoms, giving a binuclear lantern‐like structure. The pyrazine molecules occupy the two axial coordination sites. The phenyl rings are tilted by ca 10° with respect to the attached carboxylate groups. The pyrazine planes have a torsion angle of ca 19° around the Rh—N bond with respect to the plane of the nearer carboxylate group and are not coplanar with the Rh—Rh bond. 相似文献
72.
The synthesis of CF(3)OC(O)OOC(O)F is accomplished by the photolysis of a mixture of (CF(3)CO)(2)O, FC(O)C(O)F, CO, and O(2) at -15 degrees C using a low-pressure mercury lamp. The new peroxide is obtained in pure form in low yield after repeated trap-to-trap condensation and is characterized by NMR, IR, Raman, and UV spectroscopy. Geometrical parameters were studied by ab initio methods [B3LYP/6-311+G(d)]. At room temperature, CF(3)OC(O)OOC(O)F is stable for many days in the liquid or gaseous state. The melting point is -87 degrees C, and the boiling point is extrapolated to 45 degrees C from the vapor pressure curve log p = 8.384 - 1715/T (p/mbar, T/K). A possible mechanism for the formation of CF(3)OC(O)OOC(O)F is discussed, and its properties are compared with those of related compounds. 相似文献
73.
The 1H NMR spectra of rifamycin S in different solvents and at different temperatures strongly suggest the existence of a dominant conformer. The nine dihedral angles of the ansa chain from C-28 to C-19, considered conformationally flexible, were obtained from the vicinal interproton coupling constants by the Karplus equation and the proper alternative for each of them compares well with the corresponding values given by X-ray analysis in solid state.All the possible conformations derivable from the intrinsic alternatives of the NMR method were calculated for the ansa chain between C-28 and C-19 and, by applying geometrical considerations, such as closure of the polygonal path of the ansa and the steric incompatibility between the various atoms of the ansa and of the chromophore, only two of them appeared real. Thus, NMR spectroscopy can be used for studying the conformation of the ansa chain of rifamycins in solution. 相似文献
74.
We study the properties of a one-dimensional (1D) granular gas consisting of N hard rods on a line of length L (with periodic boundary conditions). The particles collide inelastically and are fluidized by a heat bath at temperature Tb and viscosity gamma. The analysis is supported by molecular dynamics simulations. The average properties of the system are first discussed, focusing on the relations between granular temperature Tg=mv2, kinetic pressure, and density rho=N/L. Thereafter, we consider the fluctuations around the average behavior obtaining a slightly non-Gaussian behavior of the velocity distributions and a spatially correlated velocity field; the density field displays clustering: this is reflected in the structure factor which has a peak in the k approximately 0 region suggesting an analogy between inelastic hard core interactions and an effective attractive potential. Finally, we study the transport properties, showing the typical subdiffusive behavior of 1D stochastically driven systems, i.e., approximately Dt(1/2), where D for the inelastic fluid is larger than the elastic case. This is directly related to the peak of the structure factor at small wave vectors. 相似文献
75.
6-Trifluoromethyl-12-acylindolo[1,2-c]quinazolines are prepared in high yield through the palladium-catalyzed reaction of bis(o-trifluoroacetamidophenyl)acetylene with aryl or vinyl halides and triflates. The reaction, which tolerates a variety of important functional groups, probably involves the formation of a 3-acyl-2-(o-trifluoroacetamidophenyl)indole intermediate, followed by its cyclization to the indoloquinazoline product. [reaction: see text] 相似文献
76.
Andrs Zelcer Zulema D. Chaia Fabio D. Cukiernik Oscar E. Piro Eduardo E. Castellano 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(3):m144-m146
The title compound, catena‐poly[[tetrakis(μ‐decanoato‐κ2O:O′)diruthenium(II,III)(Ru—Ru)]‐μ‐octanesulfonato‐κ2O:O′], [Ru2(C10H19O2)4(C8H17O3S)], is an octanesulfonate derivative of the mixed‐valence complex diruthenium tetradecanoate. The equatorial carboxylate ligands are bidentate, bridging two Ru atoms to form a dinuclear structure. Each of the two independent dinuclear metal complexes in the asymmetric unit is located at an inversion centre. The octanesulfonate anion bridges the two dinuclear units through axial coordination. The alkyl chains of the carboxylate and sulfonate ligands are arranged in a parallel manner. The global structure can be seen as infinite chains of polar moieties separated by a double layer of non‐polar alkyl groups, without interdigitation of the alkyl chains. 相似文献
77.
Catalysts for Suzuki-Miyaura coupling processes: scope and studies of the effect of ligand structure
Barder TE Walker SD Martinelli JR Buchwald SL 《Journal of the American Chemical Society》2005,127(13):4685-4696
Suzuki-Miyaura coupling reactions of aryl and heteroaryl halides with aryl-, heteroaryl- and vinylboronic acids proceed in very good to excellent yield with the use of 2-(2',6'-dimethoxybiphenyl)dicyclohexylphosphine, SPhos (1). This ligand confers unprecedented activity for these processes, allowing reactions to be performed at low catalyst levels, to prepare extremely hindered biaryls and to be carried out, in general, for reactions of aryl chlorides at room temperature. Additionally, structural studies of various 1.Pd complexes are presented along with computational data that help elucidate the efficacy that 1 imparts on Suzuki-Miyaura coupling processes. Moreover, a comparison of the reactions with 1 and with 2-(2',4',6'-triisopropylbiphenyl)diphenylphosphine (2) is presented that is informative in determining the relative importance of ligand bulk and electron-donating ability in the high activity of catalysts derived from ligands of this type. Further, when the aryl bromide becomes too hindered, an interesting C-H bond functionalization-cross-coupling sequence intervenes to provide product in high yield. 相似文献
78.
Gadolinium‐Decorated Silica Microspheres as Redox‐Responsive MRI Probes for Applications in Cell Therapy Follow‐Up
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Dr. Monica Muñoz Úbeda Dr. Fabio Carniato Dr. Valeria Catanzaro Sergio Padovan Dr. Cristina Grange Dr. Stefano Porta Dr. Carla Carrera Prof. Lorenzo Tei Dr. Giuseppe Digilio 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(23):7716-7720
The redox microenvironment within a cell graft can be considered as an indicator to assess whether the graft is metabolically active or hypoxic. We present a redox‐responsive MRI probe based on porous silica microparticles whose surface has been decorated with a Gd‐chelate through a disulphide bridge. Such microparticles are designed to be interspersed with therapeutic cells within a biocompatible hydrogel. The onset of reducing conditions within the hydrogel is paralleled by an increased clearance of Gd, that can be detected by MRI. 相似文献
79.
The reaction of esterification of benzoic acid with benzyl chloride was chosen as a model reaction to study the esterification by SN2 promoted by tertiary amine as deprotonating agent. The use of ionic liquid (IL) 1,3-dimethylimidazolium methanesulfonate [MMIm][OMs] as reaction medium has proven to give quantitative yield of the ester, but interestingly the reaction does occur even in solvent-free conditions, where the acid + the amine form a liquid system (a protic IL) in situ. This last methodology was extended to several carboxylic acids in conditions of atom economy (i.e., without excess of any reagent), giving moderately good yields of esters (54–78%) recovered by weight in pure form. 相似文献
80.
Maria Ana Castro Adrian E. Roitberg Fabio D. Cukiernik 《Journal of computational chemistry》2013,34(15):1283-1290
A classical molecular mechanics force field, able to simulate coordination polymers (CP) based on ruthenium carboxylates (Ru2(O2CReq)4Lax) (eq = equatorial group containing aliphatic chains, Lax= axial ligand), has been developed. New parameters extracted from experimental data and quantum calculations on short aliphatic chains model systems were included in the generalized AMBER force field. The proposed parametrization was evaluated using model systems with known structure, containing either short or long aliphatic chains; experimental results were reproduced satisfactorily. This modified force field, although in a preliminary stage, could then be applied to long chain liquid crystalline compounds. The resulting atomistic simulations allowed assessing the relative influence of the factors determining the CP conformation, determinant for the physical properties of these materials. © 2013 Wiley Periodicals, Inc. 相似文献