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51.
Simon G. Bott Ulrich Kynast Jerry L. Atwood 《Journal of inclusion phenomena and macrocyclic chemistry》1986,4(3):241-246
18-crown-6 reacts with TiCl3 in CH2Cl2 to form a complex in which the crown ether functions as a tridentate ligand. Addition of moist hexane affords a molecular complex in which the crown ether functions as a bidentate ligand. A water molecule is bonded directly to the titanium atom and is further hydrogen bonded to three of the oxygen atoms of the crown. The deep blue crystals of the CH2Cl2 adduct belong to the monoclinic space groupP21/n witha=13.481(8),b=8.021(5),c=21.425(9) Å, =97.32(5)°, and
calc = 1.51 g cm–3 forZ=4. Refinement led to a conventionalR value of 0.040 based on 873 observed reflections. The Ti–O bond distances for the crown oxygen atoms are 2.123(8) and 2.154(9) Å, while the oxygen atom of the water molecule is bonded at 2.072(8) Å. The octahedral coordination sphere of the titanium atom is completed by the three chlorine atoms at distances of 2.340(5), 2.352(4), and 2.373(4) Å.
Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82034 (10 pages). 相似文献
52.
Ulrich Schindewolf 《Angewandte Chemie (International ed. in English)》1978,17(12):887-901
Electrons produced in a gaseous, liquid, or solid solvent are called dissolved electrons or excess electrons. These excess electrons can exist as quasi-free particles of high mobility in a delocalized state, comparable with electrons in a metal; or as bound particles of low mobility they can be localized within narrow limits—in a solvent cavity formed by repulsive forces. Localized electrons can also be solvated like normal ions. Characteristically, such solvated electrons exhibit broad and extensive absorption spectra in the visible to near infrared spectral range. The localized and delocalized states of the excess electrons can be in equilibrium with each other, such that a continuous transition of the properties between the limiting extremes can be observed. The reactions of the excess electrons with suitable acceptors (substrates) are initiated by an attachment-detachment equilibrium A + e? ? A? which is followed by further chemical rearrangements. The rate constants of these reactions vary by more than 15 powers of ten depending on the substrates and the solvents. Most of the properties of excess electrons in solution can be interpreted by means of a model which is easily understandable but quantitatively evaluated only with considerable effort. 相似文献
53.
THF-gramicidin hybrids 2-4 with the L-THF amino acid 1 in positions 11 and 12 and compounds 5-8 with the D-THF amino acid ent-1 in positions 10 and 11 were synthesized and their ion channel properties were studied by single-channel-current analysis. The replacement of positions 11 and 12 by the L-THF amino acid 1 gave a strongly reduced channel performance. In contrast, replacement of positions 10 and 11 by the D-THF amino acid ent-1 gave rise to new and interesting channel properties. For the permeability ratios, the ion selectivity shifts from Eisenman I towards Eisenman III selectivity and the channels display ms-dynamics. Most remarkable is the asymmetric compound 8, which inserts selectively into a DPhPC membrane and displays voltage-directed gating dynamics. 相似文献
54.
Darbost U Rager MN Petit S Jabin I Reinaud O 《Journal of the American Chemical Society》2005,127(23):8517-8525
The host-guest properties of calix[6]tren 1 have been evaluated. The receptor is based on a calix[6]arene that is covalently capped at the narrow rim by a tren unit. As a result, the system presents a concave hydrophobic cavity with, at its bottom, a grid-like nitrogenous core. Despite its well-defined cavity and opening to the outside at the large rim, 1 did not behave as a good receptor for neutral molecules in chloroform. However, it exhibited efficient endo-complexation of ammonium guests. By contrast, the per-protonated host, 1.4H(+), behaved as a remarkable receptor for small organic molecules. The complexation is driven by a strong charge-dipole interaction and hydrogen bonds between the polar guest and the tetracationic cap of the calixarene. Finally, coordination of Zn(2+) to the tren core led to the asymmetrization of calixarene cavity and to the strong but selective endo-binding of neutral ligands. This study emphasizes the efficiency of a receptor presenting a concave hydrophobic cavity that is polarized at its bottom. The resulting combination of charge-dipole, hydrogen bonding, CH-pi, and van der Waals interactions highly stabilizes the supramolecular architectures. Also, importantly, the tren cap allows the tuning of the polarization, offering either a basic (1), a highly charged and acidic (1.4H(+)), or a coordination (1.Zn(2+)) site. As a result, the system proved to be highly versatile, tunable, and interconvertible in solution by simple addition of protons, bases, or metal ions. 相似文献
55.
Nina Ulrich 《Analytical and bioanalytical chemistry》1998,360(7-8):797-800
An on-line method for the analysis of Sb(III), Sb(V) and trimethylstiboxide (TMSbO) is presented. The separation is performed
using ion chromatography (IC) on a strong anion-exchange column with phthalic acid plus 2% acteone at pH 5 as mobile phase.
The chromatographic system is coupled to an ICP-MS as detector. The influence of different complexing agents on the chromatographic
behavior of the antimony species is studied. Rather stable complexes of Sb(III) seem to be formed with citrate and tartrate
under the experimental conditions. TMSbO forms a dianionic species with citrate in contrast to the otherwise monoanionic complex.
Received: 31 Juli 1997 / Revised: 8 December 1997 / Accepted: 11 December 1997 相似文献
56.
57.
N(SCl)2⊕ [MoCl5(NSCl)]?, a Chlorothionitrene Complex of Molybdenum (VI) . The title compound is formed together with MoCl3(N3S2) by the reaction of MoCl4 or MoCl5 with (NSCl)3 in CH2Cl2. The black, crystalline compound was characterized by its i.r. spectrum and an X-ray crystal structure determination. N(SCl)2⊕[MoCl5(NSCl)]? crystallizes in the monoclinic space group P21/n with four formula units per unit cell. The lattice constants are a = 716.3, b = 1627.4, c = 1178.9 pm and β = 100.90°. The [MoCl5(NSCl)]? ion posseses an almost linear Mo = N = S grouping with bond lengths that can be interpreted as double bonds. Crystal data for AsPh4[MoCl5(NSCl)] are reported. 相似文献
58.
The mer‐octahedral complexes(2‐carbonyl)(4‐Me)(6‐tBu)phenolato[C,O]hydridotris(trimethylphosphine)cobalt(III) ( 1 ) or ‐(1‐carbonyl)(2‐oxo)(1,2‐diphenylethene)[C,O]hydridotris(trimethylphosphine)cobalt(III) ( 2 ) via formal insertion of propynoic acid ethyl ester into Co‐H functions afford pentacoordinate vinylcobalt(III) 3 and 4 , respectively, that are diamagnetic and attain a square pyramidal structure as exemplified by an X‐ray diffraction analysis of 3 . 相似文献
59.
The synthesis of the indoles 7 , 15 , 16 with a 3-methoxyphenyl group, attached via an α-side chain of 1,2,or 3 CH2 units, is reported. These compounds, after appropriate protection at C(3), were transformed into the N-[(dimethylamino)methyl]indoles 22 , 23 , and 24 , respectively. When treated with AcCl, these N-Mannich bases gave, in two cases, stable N-(chloromethyl)indoles 25 and 26 . In the presence of SnCl4, ring closure occurred via electrophilic attack of 1-methylideneindolium ions on the methoxyphenyl group. Formation of seven-membered rings (→ 27 , 28 ) and eight-membered rings (→ 29 ) was found to be a favorable process. Cyclization to six-membered rings did not occur within this series. 相似文献
60.
Sila-analoguesA 2 andB 2 of two drugs from the benzhydryl ether class, chlorphenoxamine and clofenetamine, were synthesized for the first time by the steps shown in scheme 1. They and their precursors I–VI were characterized by their physical (Table 1) and chemical properties and their structures confirmed by n.m.r., mass and infrared spectrocopy (Tables 2–5). Their physiological effects were investigated and compared with those of the carbon analogues (Chapter 5).
1. Mitt.:R. Tacke undU. Wannagat, Mh. Chem.106, 1005 (1975).
Mit Auszügen aus der DissertationR. Tacke, Techn. Univ. Braunschweig 1974. 相似文献
1. Mitt.:R. Tacke undU. Wannagat, Mh. Chem.106, 1005 (1975).
Mit Auszügen aus der DissertationR. Tacke, Techn. Univ. Braunschweig 1974. 相似文献