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201.
al-Ktaifani MM Bauer W Bergsträsser U Breit B Francis MD Heinemann FW Hitchcock PB Mack A Nixon JF Pritzkow H Regitz M Zeller M Zenneck U 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(11):2622-2633
Several independent synthetic routes are described leading to the formation of a novel unsaturated tetracyclic phosphorus carbon cage compound tBu4C4P6 (1), which undergoes a light-induced valence isomerization to produce the first hexaphosphapentaprismane cage tBu4C4P6 (2). A second unsaturated isomer tBu4C4P6 (9) of 1 and the bis-[W(CO)5] complex 13 of 1 are stable towards similar isomerization reactions. Another starting material for the synthesis of the hexaphosphapentaprismane cage tBu4C4P6 (2) is the trimeric mercury complex [(tBu4C4P6)Hg]3 (11), which undergoes elimination of mercury to afford the title compound 2. Single-crystal X-ray structural determinations have been carried out on compounds 1, 2, 9, 11, and 13. 相似文献
202.
Time-resolved laser-induced fluorescence (TRLIF) has been used to study the interaction of uranyl ion with sodium dodecyl sulfate (SDS) micelles in H(3)PO(4) 1 M. The titration curve consists of two curved regions with different slopes, one of them more pronounced at low concentration of SDS and the other, with a less pronounced positive slope at larger [SDS] until a plateau is reached. The fluorescence quenching of uranyl ion by para-substituted phenol compounds was studied by TRLIF and steady-state emission intensity measurements. The results were interpreted in terms of binding of phenolic compounds to the micelle. The binding constant (K(Q)) as well as the entrance and exit rate constants were determined for all the quenchers used. 相似文献
203.
Ring-closing metathesis (RCM) is the key step in a recently reported synthesis of salicylihalamide and related model compounds. Experimentally, the stereochemistry of the resulting cycloolefin (cis/trans) depends strongly on the substituents that are present in the diene substrate. To gain insight into the factors that govern the observed stereochemistry, density functional theory (DFT) calculations have been carried out for a simplified dichloro(2-propylidene)(imidazole-2-ylidene)ruthenium catalyst I, as well as for the real catalyst II with two mesityl substituents on the imidazole ring. Four model substrates are considered, which are closely related to the systems studied experimentally, and in each case, two pathways A and B are possible since the RCM reaction can be initiated by coordination of either of the two diene double bonds to the metal center. The first metathesis yields a carbene intermediate, which can then undergo a second metathesis by ring closure, metallacycle formation, and metallacycle cleavage to give the final cycloolefin complex. According to the DFT calculations, the stereochemistry is always determined in the second metathesis reaction, but the rate-determining step may be different for different catalysts, substrates, and pathways. The ancillary N-heterocyclic carbene ligand lies in the Ru-Cl-Cl plane in the simplified catalyst I, but is perpendicular to it in the real catalyst II, and this affects the relative energies of the relevant intermediates and transition states. Likewise, the introduction of methyl substituents in the diene substrates influences these relative energies appreciably. Good agreement with the experimentally observed stereochemistry is only found when using the real catalyst II and the largest model substrates in the DFT calculations. 相似文献
204.
[reaction in text] In a chiral auxiliary based method C-glycosylated amino acids can be obtained by a 1,3-dipolar cycloaddition of a chiral glycine equivalent and C-1 allyl- or vinyl-derived carbohydrate building blocks as the key step. The products are formed regio- and diastereoselectively. Reductive cleavage of the N-O bond of the isoxazolidine and of the chiral auxiliary leads to C-glycosylated amino acids. The use of (-)-menthone to (+)-menthone as the auxiliary leads to the corresponding diastereomers. 相似文献
205.
It is possible to determine very high concentrations of nickel photometrically by means of ethylenediaminetetra-acetic acid, by working at a pH between 4.55 and 6.82. The absorption curves obtained for this complex are very reproducible; for these measurements an Elko II apparatus with filter S57E is used. High concentrations of ammoniacal salts hinder the measurement. The formation of the complex is not influenced by the anion of the compound of nickel used. The Lambert-Beer law is followed for strengths of nickel of 40 — 5000 mg/100 ml. This procedure is convenient for alloys rich in nickel. 相似文献
206.
Mehrzad Mehran William J. Cooper Nahid Golkar Michael G. Nickelsen Eric R. Mittlefehldt Edward Guthrie Walter Jennings 《Journal of separation science》1991,14(11):745-750
The retention behavior of a heterogeneous group of solutes has been examined on seven different stationary phases under isothermal and temperature-programmed conditions. Both ΔHv (enthalpy of solute vaporization from the stationary phase) and ΔSv (entropy of solute vaporization from the stationary phase) values were determined for each solute – stationary phase combination under isothermal conditions. Both program rate and carrier gas velocity were shown to affect solute elution order. Unless these and other experimental factors discussed are controlled, column equivalency studies based on solute elution order have dubious value. 相似文献
207.
Ga8Ir4B – a Gallium Iridium Boride with isolated, nearly square planar Ir4B Groups in a Structure derived from the CaF2 Type The new compound Ga8Ir4B (tetragonal, I41/acd, a = 853.69(2) pm, c = 2 105.69(6) pm, Z = 8, 614 reflections, 31 parameters, R = 0.034) was prepared by reaction of the elements at 1 100°C. The structure is derived from the CaF2 type. It contains isolated Ir4B groups with boron in an unusual, nearly square planar coordination. 相似文献
208.
Thomas E. Sorensen Walter B. England David M. Silver E. Otto Steinborn 《Theoretical chemistry accounts》1992,84(1-2):1-19
Summary Many-body perturbation theory is derived for chemical bonds. Paired quasiparticles represent the bonds. Products of the paired quasiparticles define a model Bardeen-Cooper-Schrieffer function. The pairing force is added as a model interaction to the self-consistent problem. The starting model is based on valency and adiabatic symmetry correlation. Symmetries are enforced by the model Hamiltonian. Perturbative corrections are expressed as ordinary Feynman diagrams. The number of diagrams needed is the same as for particle-hole theory.This work was supported in part by the U.S. Department of the Navy, Space and Naval Warfare Systems Command under Contract N00039-89-C-0001, and in part by NATO Research Grant 1861. It was presented, in part, at the A.C. Wahl Memorial Session, Molecular Spectroscopy Symposium, Columbus, Ohio, 1984; and Midwest Theoretical Chemistry Conference, Milwaukee, Wisconsin, 1985. 相似文献
209.
Walter Simon 《General Relativity and Gravitation》1984,16(5):465-476
For stationary, asymptotically flat solutions of Einstein's equations, covariant functionals of the metric variables are defined which characterize the Kerr metric uniquely. For instance, we obtain a generalization of the Bach tensor to stationary metrics, which vanishes if and only if the solution is Kerr. We also give a new interpretation of the Schwarzschild-to-Kerr-transformation. Our results might be applicable to simplify the proof of the uniqueness theorem for stationary black holes. 相似文献
210.
Wolfgang Hnle Walter Schmettow Karl Peters Jen‐Hui Chang Hans Georg von Schnering 《无机化学与普通化学杂志》2004,630(12):1858-1862
The novel ternary polyphosphides M4P21I (M = K, Rb) have been synthesized from the elements in single crystalline form, representing further examples for the formation of mixed crystals between simple salts and binary phosphides. They form as ruby‐red platelets and dark‐red prisms, respectively, and are only slightly sensitive to moisture and oxygen. The compounds are isotypic (Ccmm (no 63); Z = 4; oP104; K4P21I: a = 12.853Å; b = 21.795Å; c = 9.748Å; 1168 hkl, R = 0.033; Rb4P21I: a = 13.281Å; b = 21.868Å; c = 9.771Å; 777 hkl, R = 0.053) and feature corrugated 2D networks formed from two different types of polymerized P7 units. The networks form large cavities filled by M+ and I‐ ions. Zigzag chains of condensed trigonal M6 prisms, centered by the I‐ anions, separate the polyphosphide nets. The mean homoatomic P‐P bond length (d = 2.216Å) corresponds to a P‐P single bond. However, the individual P‐P distances vary with position and function (2.126 ‐ 2.247Å) and these are compared with those of the isolated P21‐3 anion. 相似文献