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11.
Jesús Valdés-Martínez Ruben A. Toscano Roberto Salcedo Raymundo Cea-Olivares Adrian Meléndez 《Monatshefte für Chemie / Chemical Monthly》1990,121(8-9):641-647
Summary The crystal and molecular structure of salicylaldehyde semicarbazone was obtained by single crystal X-ray diffraction. The O atom of the semicarbazone fragment isanti to the N atom of the hydrazinic group. The distribution of bond lengths in the semicarbazone fragment indicates delocalization of the -electrons. The crystal structure is stabilized by intra- and intermolecular hydrogen bonds.
Semicarbazone und Thiosemicarbazone, 12. Mitt.: Die Kristallstruktur des Salicylaldehyd-Semicarbazons
Zusammenfassung Die Kristallstruktur und die molekulare Struktur des Salicylaldehyd-Semicarbazons wurde über Einkristall-Röntgenstreuung ermittelt. Das O-Atom des Semicarbazonteils stehtanti zum N-Atom der Hydrazin-Gruppierung. Die Bindungslängen in der Semicarbazoneinheit zeigen eine Delokalisierung der -Elektronen an. Die Geometrie der Verbindung wird durch stabilisierende intra- und intermolekulare Wasserstoffbrückenbindungen bestimmt.相似文献
12.
[reaction: see text] The photochemistry of N-acyl-5,7-dinitroindoline (1) was studied in acetonitrile using nanosecond time-resolved infrared (TRIR) spectroscopy. Upon photolysis, two nearly but not completely overlapping sets of transient IR bands are observed that are assigned to two non-interconvertible conformers of mixed acetic nitronic anhydride 7. While syn-7 reverts rapidly to 1, anti-7 is long-lived and is able to acylate amines. Results of density functional theory calculations support conclusions based on experimental TRIR data. 相似文献
13.
[reaction: see text] Treatment of 1,4-dilithio-1,3-butadiyne (1) with dichalcogenides RSSR or RSeSeR affords dithio- and diseleno-1,3-butadiynes (2, 3), perthio- and perseleno-[3]-cumulenes (4, 5), perthio- and perseleno-1,3-butadienes (6, 7), and/or perthio- and perseleno-but-1-ene-3-ynes (8, 9). The products can be controlled by stoichiometry and temperature, by the presence or absence of oxygen, and by choice of the "R" group. By X-ray crystallography, hexa(methylthio)-1,3-butadiene is highly twisted, with a torsion angle [Phi(CCCC)] of 84.7 degrees and an elongated C(2)-C(3) distance of 1.484(3) A. 相似文献
14.
Payne RJ Toscano MD Bulloch EM Abell AD Abell C 《Organic & biomolecular chemistry》2005,3(12):2271-2281
Aromatic analogues of chorismate were synthesised as potential inhibitors of anthranilate synthase. Molecular modelling using GOLD2.1 showed that these analogues docked into the active site of Serratia marcescens anthranilate synthase in the same conformation as chorismate. Most compounds were found to be micromolar inhibitors of S. marcescens anthranilate synthase. The most potent analogue, 3-(1-carboxy-ethoxy)-4-hydroxybenzoate (K(I) 3 microM), included a lactyl ether side chain. This appears to be a good replacement for the enol-pyruvyl side chain of chorismate. 相似文献
15.
Diana Cruz-Garritz Juventino Garcia-Alejandre Hugo Torrens Cecilio Alvarez Raul A. Toscano Rene Poilblanc Alain Thorez 《Transition Metal Chemistry》1991,16(1):130-135
Summary The thiolato-bridged dinuclear compounds [Rh(-SR)-(COD)]2, where R=p-C6HF4 (1),p-C6H4F (2) and CF3 (3), are obtained from the chloro-bridged analogue by ligand exchange.Compound (1) crystallizes in the space group P1 with a=9.740(3)Å, b=11.642(4)Å, c=13.997(6)Å, =103.87(3)°, =106.98(3)° and =105.10(2)°; z=2. In this dinuclear molecule both Rh atoms have a square planar coordination sharing one edge, namely the two sulphur bridging atoms. The Rh—Rh separation of 2.96 Å is consistent with at most a very weak metal-metal interaction. Upon addition of CO the dimeric [Rh(-SR)(CO)2]2 (4), (5) and (6) are obtained, but addition of PPh3 affords the monomeric species [Rh(SR)(PPh3)-(COD)] (7), (8) and (9). Reactions of the dimeric tetracarbonyl derivatives with PPh3 vary with the nature of R; [Rh(-SR)(PPh3)(CO)]2 is obtained when R=p-C6H4F (10) and CF3 (11) but monomeric [Rh(SR)-(PPh3)(CO)2] (12) is produced when R=p-C6HF4. The latter mononuclear compounds, with R=p-C6H4F (13) and CF3 (14), are also formed by reaction of [Rh(SR)-(PPh3)(COD)] with CO. 相似文献
16.
Jang SS Lin ST Cagin T Molinero V Goddard WA 《The journal of physical chemistry. B》2005,109(20):10154-10167
We propose a new material consisting of a dendrion copolymer formed from (a) a water-soluble dendritic polymer and (b) a hydrophobic backbone. Using molecular dynamics simulations techniques, we determine the structure and dynamics of the dendrion formed by second-generation Fréchet polyaryl ethereal dendrimer as the hydrophilic component and linear polytetrafluoroethylene (PTFE) as the hydrophobic polymer, with 5 and 10 wt % of water. We find that this material produces a well-developed nanoscale structure in which water forms a continuous nanophase, making this new family of compounds promising candidates for applications in fuel cell membranes. We find that the water molecules are incorporated into the dendrimer block of the copolymer to form a nanophase-segregated structure. The well-developed nanophase-segregated structures rendered by this material have characteristic dimensions of segregation ( approximately 30 Angstrom) and dendrimer conformational properties that are independent of water content. Calculations of water dynamics and proton transport in these nanophase-segregated structures indicate that the dendrion copolymer membrane with 10 wt % of water content has a water structure and transport properties equivalent to that of the hydrated Nafion membrane with 20 wt % of water content. 相似文献
17.
Labile metal species in aquatic humic substances (HSs) were characterized by ion exchange on cellulose phosphate (CellPhos) by applying an optimized batch procedure. The HSs investigated were pre-extracted from humic-rich waters by ultrafiltration and a resin XAD 8 procedure. The HS-metal species studied were formed by complexation with Cd(II), Ni(II), Cu(II), Mn(II) and Pb(II) as a function of time and the ratio ions to HSs. The kinetics and reaction order of this exchange process were studied. At the beginning (<3 min), the labile metal fractions are separated relatively quickly. After 3 min, the separation of the metal ions proceeds with uniform half-lives of about 12-14 min, revealing rather slow first-order kinetics. The metal exchange between HSs and CellPhos exhibited the following order of metal lability with the studied HSs: Cu > Pb > Mn > Ni > Cd. The required metal determinations were carried out by atomic absorption spectrometry. 相似文献
18.
García-Orozco I López-Cortés JG Ortega-Alfaro MC Toscano RA Penieres-Carrillo G Alvarez-Toledano C 《Inorganic chemistry》2004,43(26):8572-8576
The paper describes the synthesis and structural characterization of four novel copper(I) complexes [CuL(PPh(3))(2)] (L = 3-hydroxy-3-(p-R-phenyl)-2-propenedithioate). In addition, a tautomeric equilibrium in solution was found and Hammett correlations with (13)C NMR parameters were studied. The structure of one complex was fully established by X-ray diffraction analysis. 相似文献
19.
Summary A new transition state algorithm incorporated into the density functional code deMon, has been used to study thetrans cis-hydroxymethylene andtrans-hydroxymethylene formaldehyde isomerization processes and to localize the transition state for the decomposition of 1,3-diazacyclobutane to methyleneimine. Calculations have been performed using both local (LSD) and nonlocal spin density (NLSD) gradient-corrected approximations. Two different basis sets of small and large size have been used for the study in order to analyze the effect of the basis set dimension other than that of the nonlocal corrections on the activation energy barrier value. The results seem to confirm that density functional methods can be considered practical and reliable tools for the localization of transition states. 相似文献
20.
Fernández-G Juan M. Ruíz-Ramírez Oscar L. Toscano Rubén A. Macías-Ruvalcaba Norma Aguilar-Martínez Martha 《Transition Metal Chemistry》2000,25(5):511-517
Three Schiff base copper(II) complexes have been prepared and characterized by elemental analysis, mass spectra, i.r., electronic spectra, eff and X-ray crystal structures. Cyclic voltammetry studies on the complexes indicate a dependence of the cathodic potentials upon electronic effects, but independence on the solid state structure. 相似文献