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31.
The model of two interacting ethylene molecules having D
2h symmetry was studied using generalized Hückel method. The validity of - separation was tested on this model. The general character of the ground state and lower lying excited states of the model was discussed and the implications drawn concerning transannular interaction and excimer formation. The values obtained for the dissociation energy of the first excited state of our model and corresponding equilibrium intermolecular distance are of right order of magnitude.
Zusammenfassung Mittels der verallgemeinerten Hückel-Methode wurde das Modell von zwei Äthylenmolekülen mit der Symmetrie D 2h studiert. An diesem Modell wurde die Gültigkeit der - -Separation geprüft. Der allgemeine Charakter des Grundzustandes und der niedriger liegenden angeregten Zustände des Modells wird erörtert und die Folgerungen in Bezug auf transannulare Wechselwirkung und Excimer-Entstehung diskutiert. Die erhaltenen Werte für die Dissoziationsenergie des ersten angeregten Zustandes von unserem Modell und den entsprechenden intermolekularen Gleichgewichtsabstand haben die richtige Größenordnung.
Résumé Le modèle à symétrie D 2h de deux molécules d'éthylène en interaction a été étudié en utilisant la méthode généralisée de Hückel. On a examiné la validité de la séparation - sur ce modèle. Le caractère général de l'état fondamental et celui des états excités inférieurs du modèle furent discutés et on a fait des déductions sur l'interaction transannulaire et sur la formation d'«excimères». Les valeurs obtenues pour l'énergie de dissociation du premier état excité de notre modèle et la distance intermoléculaire d'équilibre corréspondante ont l'ordre de magnitude correct.相似文献
32.
Martina Nveke Peter G. Jones Armand Blaschette Dietmar Schomburg Heiko K. Cammenga Matthias Epple 《无机化学与普通化学杂志》1993,619(6):1027-1036
Polysulfonyl Amines. XLI. A Silver(I) Hydrate with an Unusual Composition: Characterization of Tetrakis(dimesylamido)aquatetrasilver(I) [Ag4(N)SO2CH3)2}4(H2O)] by X-Ray Diffraction and Thermal Analysis The title compound is obtained by crystallizing AgN(SO2CH3)2 from water at room temperature. Crystallographic data (at ?95°C): Triclinic space group P1 , a = 864.6(4), b = 1 211.2(5), c = 1 399.1(5) pm, α = 90.97(3), β = 90.90(3), γ = 98.25(4)°, V = 1.4496 nm3, Z = 2, Dx = 2.608 Mg m?3. The four independent silver atoms and the water molecule form zigzag chains Ag(1)-Ag(2)-(μ-H2O)-Ag(3) …? Ag(4) …? Ag(1′) with distances Ag(1)-Ag(2) 309.7, Ag(2)-O(w) 241.8, O(w)-Ag(3) 241.4, Ag(3) …? Ag(4) 342.9, Ag(4) …? Ag(1′) 361.4 pm. The catenated silver atoms are further connected by the dimesylamide anions acting as tridentate bridging (α-O, N, ω-O)-ligands. The resulting strands are interconnected into layers through one O(S)-Ag′ contact (247 pm) and one hydrogen bond O(w)-H(l) …? O′(S) per repeating unit. Between the layers, a weak O(S) …? Ag″ interaction (271 ptn) and a hydrogen bond O(w)-H(2) …? O(S) per repeating unit are observed. The silver atoms Ag(l) to Ag(4) display the coordination numbers 5 [NO,Ag(2), distorted trigonal bipyramid], 5[NO2,O(w)Ag(I), distorted trigonal bipyramid], 5[O4,O(w), trigonal bipyramid], and 2 + 1 (N2, li-near; plus a secondary Ag …? 0 contact). The dehydration of the title compound and a solid-solid phase transformation in anhydrous AgN(SO2CH3)2, were quantitatively investigated by thermoconductometry and time- and temperature-resolved X-ray diffractometry (TXRD). 相似文献
33.
Peter Segl'a Martina Palicov Dusan Miklos Marian Koman Milan Melník Maria Korabik Jerzy Mrozinski Tadeusz Glowiak Markku R. Sundberg Peter Lnnecke 《无机化学与普通化学杂志》2004,630(3):470-478
Synthesis and characterization of seven new complexes [Cu(2‐MeSnic)2(CH3OH)]2 (where 2‐MeSnic is 2‐methylthionicotinate), [Cu(2‐MeSnic)2L2]2 (where L is pyridine — py, ethylnicotinate — Etnic and butylnicotinate — Bunic), [Cu(2‐MeSnic)2L2(H2O)2] (where L is py and nicotinamide — nia) and [Cu(2‐MeSnic)2(N‐Menia)2(H2O)2]·2H2O (where N‐Menia is N‐methylnicotinamide) are reported. The characterization were based on elemental analysis, infrared, electronic and EPR spectra, and magnetic susceptibility measurements over a temperature range of 1.8 — 300 K or 70 — 300 K. Three complexes of different type were studied by X‐ray analysis. The molecule of [Cu(2‐MeSnic)2(CH3OH)]2 has dimeric paddle‐wheel cage structure with a tetragonal pyramidal arrangement around CuII. The dimer results from the fact that carboxyl groups of four 2‐MeSnic anions function as bridging in a syn‐syn arrangement. On the other hand [Cu(2‐MeSnic)2(py)2]2 forms dimers with hexacoordinated CuII atoms in highly distorted coordination octahedra, each with two oxygen atoms of bridging carboxyl groups in an anti‐anti arrangement of two 2‐MeSnic anions, with two oxygen atoms of one asymmetrically chelating 2‐MeSnic anion and with two nitrogen atoms of two pyridine ligands. The temperature independent EPR spectrum for this complex exhibits an axial signal which corresponds to almost isolated S = 1/2 magnetic ions. Magnetic data for the dimer show a weak antiferromagnetic interaction between the two metal ions with J = —0.65 cm—1. The CuII atom in complex [Cu(2‐MeSnic)2(py)2(H2O)2] is hexacoordinated in an elongated centrosymmetrical tetragonal‐bipyramidal arrangement (4 + 2). Based on the molecular structure the electronic, infrared, electron paramagnetic resonance spectra and magnetic properties are discussed and stereochemistry as well as the mode of ligand coordination in new solid complexes under study have been determined. 相似文献
34.
Sébastien L.X. Martina 《Tetrahedron letters》2004,45(16):3279-3282
Novel solid-supported phosphonate reagents have been prepared and evaluated for the synthesis of α,β-unsaturated esters with a preference for the Z-alkene. The optimal reagent was a hybrid of both Still-Gennari and Ando reagents, and showed good to high yields and fair to good Z-selectivity for the conversion of both aliphatic and aromatic aldehydes. 相似文献
35.
Angel Alberola Celia Andrs Alfonso Gonzlez Ortega Rafael Pedrosa Martina Vicente 《Journal of heterocyclic chemistry》1987,24(3):709-713
Unsymmetrically substituted β-aminoenones react with malononitrile, cyanomethylphenylsulfone, benzoyl-acetonitrile and ethyl cyanoacetate, in very mild conditions, to yield regiospecifically 3-functionalized 2(1H)-pyridones in high yields. 相似文献
36.
The method for constructing hybrid orbitals described earlier is now used for the analysis of CNDO/2 wave functions of molecules containing nitrogen atoms in order to get information on the type of hybridization of nitrogen lone pair orbitals in various compounds. 相似文献
37.
The “solvophobic” effect is the tendency of solute particles to cluster as the attractive interaction between solvent particles is strengthened. The potentials of mean force in the hypernetted chain approximation have been obtained for a simple fluid mixture consisting of two hard spheres immersed in a hard core/Yukawa tail solvent. The results clearly exhibit features attributable to the “solvophobic” effect. 相似文献
38.
Pol VG Grisaru H Gedanken A 《Langmuir : the ACS journal of surfaces and colloids》2005,21(8):3635-3640
The method of ultrasound irradiation is used for anchoring metallic nanocrystals (Ag, Au, Pd, and Pt) onto the surface of polystyrene spheres. In former studies, almost all the sonochemically prepared, coated metallic nanomaterials were formed as amorphous nanoparticles (Pol, V. G.; et al. Langmuir 2002, 18, 3352; Pol, V. G.; et al. Chem. Mater. 2003, 15, 1111; Zhong, Z. Y.; et al. Chem. Mater. 1999, 11 (9), 2350; Pol, V. G.; et al. Chem. Mater. 2003, 15, 1378), which were coated on various substrates (silica spheres, carbon spherules, titania, and alumina). On the other hand, the noble metal nanoparticles deposited on polystyrene spheres via ultrasound irradiation yielded nanocrystalline Ag, Au, Pd, and Pt particles on the surface of polystyrene as as-synthesized materials. The sonochemical mechanism is proposed based on chemical interactions between the particles. 相似文献
39.
An extremely sensitive, reliable and simple procedure is described for the determination of physiological palladium, platinum and gold in human urine. The urine samples were adjusted to pH 4 (Pd, Au) or pH 5 (Pt), followed by conversion of the analytes to their pyrrolidinedithiocarbamate complexes. These complexes were separated from the matrix by liquid-liquid extraction into 4-methyl-2-pentanone resulting in a 25-fold enrichment. Determination was by electrothermal atomic absorption spectrometry (ET-AAS) using longitudinal inverse alternating current Zeeman-effect background correction. The limits of detection calculated from three standard deviations of the blank values were 20 ng l−1 for Pd and Au and 70 ng l−1 Pt. Within-day precision (n = 10, 5 μg l−1) ranged 5.2%–7.7%. The procedure is successfully applied to determine urinary palladium, platinum and gold in nine unexposed persons. Palladium levels in urine ranged < 20–80 ng l−1 (arithmetical MEAN=38.7 ng l−1), while gold levels ranged < 20–130 ng l−1 (36.0 ng l−1). Physiological platinum levels in urine were all < 70 ng l−1. The accuracy of the procedure was checked by analyzing a series of urine samples by a second independent method (magnetic sector field inductively-coupled plasma-mass spectrometry) in combination with UV photolysis. 相似文献
40.
Hales M Barner-Kowollik C Davis TP Stenzel MH 《Langmuir : the ACS journal of surfaces and colloids》2004,20(25):10809-10817
A polylactide (D,L-PLA) macroRAFT agent was prepared by utilizing a hydroxyl-functional trithiocarbonate as a coinitiator for the ring-opening polymerization. The length of the resultant polymer was controlled by the concentration of the coinitiator leading to the formation of two PLA polymers with M(n) = 12500 g mol(-)(1) (PDI = 1.46) and M(n) = 20500 g mol(-)(1) (PDI = 1.38) each with omega-trithiocarbonate functionality. Chain extension of PLA via the RAFT (free radical) polymerization of N-isopropyl acrylamide (NIPAAm) resulted in the formation of amphiphilic block copolymers with the PNIPAAm block increasing in size with conversion. TEM measurements of the aggregates obtained by self-organization of the block copolymers in aqueous solutions indicated the formation of vesicles. The sizes of these aggregates were influenced by the ratio of both blocks and the molecular weight of each block. The lower critical solution temperature (LCST) of the block copolymer was largely unaffected by the size of each block. UV turbidity measurements indicated a higher LCST for the block copolymers than for the corresponding PNIPAAm homopolymers. Stabilization of the vesicles was attained by a cross-linking chain extension of the PNIPAAm block using hexamethylene diacrylate. As the trithiocarbonate group was located between the PLA and PNIPAAm blocks, the chain extension resulted in a cross-linked layer between the core and corona of the vesicles. 相似文献