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  • General Chemistry  (1,786)
  • Cell & Developmental Biology  (458)
  • 1995-1999  (2,244)
  • 1996  (2,244)
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  • 1995-1999  (2,244)
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  • 1
    ISSN: 0947-6539
    Keywords: ab initio calculations ; azaenolates ; NMR chemical shifts ; peptides ; Ramachandran maps ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Structures and conformations of the azaenolate lithium salts of amides (formamide, acetamide, and N-methylacetamide) and of the dipeptide model N-formylalaninamide were investigated by means of ab initio MO theory. Four possible structures of the lithiated C-enolates of acetamide were also included in the study. All structures were calculated at the HF/6-31+G(d) and MP2(fc)/6-31 + G(d)/HF/6-31 + G(d) levels; the lithiated azaenolates of formamide were also investigated at higher theoretical levels (up to MP4(fc)/6-311 + G(d,p)/MP2(fc)/6-311 + G(d,p)). For the lithiated azaenolates of all amides investigated, the most stable structure contains a four-membered ring in which the lithium ion is complexed by the oxygen and nitrogen atoms; the substituents attached to the carbon and nitrogen atoms of the azaenolate are in a cis arrangement. The lithiated azaenolates of acetamide are predicted to be more stable than the corresponding C-enolates. To simulate solvation, calculations on complexes of the lithiated azaenolates of formamide with up to three molecules dimethyl ether were also performed, and all azaenolates of amides were also reoptimized by ab initio reaction-field calculations. Both solvation models reduce the preference for lithium-chelated cis structures. The Ramachandran maps of the dilithiated bis(azaenolate) of N-formylalaninamide (having cis or trans arrangements of the azaenolate substituents) were scanned by MNDO calculations for conformational accessible regions. Thirteen stable structures were subsequently optimized at the HF/6-31 + G(d) ab initio level. The global minimum resembles a peptide in C7 conformation, but other conformations, not known for peptides, are close in energy. The structures of dimers of the lithiated azaenolates of N-methylacetamide and of glycinaldehyde were also calculated. The NMR chemical shielding of carbon, nitrogen, and oxygen atoms in all structures were predicted ab initio by using the gauge-including atomic orbital (GIAO) method.
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  • 2
    ISSN: 0947-6539
    Keywords: alkenes ; catalysis ; dihydroxylations ; electrophilicity ; ruthenium compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oxidative ruthenium catalysis (0.07 molequiv RuCl3·(H2o)3, 1.5 molequiv NaIO4, EtOAc/CH3CH3CN/H2O 3:3:1), beyond the usual C—C bond cleavage to give dicarbonyls, has been shown to syn-dihydroxylate a wide range of alkenes (except for strained bicyclic alkenes, sterically hindered trisubstituted alkenes, and most tetrasubstituted alkenes) to give vicinal diols rapidly (within minutes) and efficiently. The minor products are the usual oxidative fission products, namely, ketones and aldehydes or carboxylic acids, and sometimes ketols. Longer reaction times lower the yields of most diols, probably owing to oxidative glycol cleavage. Reactions with substrates containing one or more electron-with-drawing groups in conjugation with or adjacent to the alkene moiety are generally slower but give better yields. The diastereoselectivity of the present “flash” dihydroxylation, anti to the existing α-stereogenic center, with cycloalkenes is excellent whereas that with acyclic alkenes is moderate to poor. Sodium metaperiodate is still the best co-oxidant for the catalytic reaction. Aqueous acetonitrile (approximately 86%) as an alternative solvent system was found to give better yields of 1,2-diols than the original solvent system in some cases.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 83-87 
    ISSN: 0947-6539
    Keywords: enzyme models ; iron complexes ; molybdenum complexes ; nitro genase ; semi-empirical calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A model for the active site of nitrogenase is suggested and examined by means of the intermediate neglect of differential overlap (INDO) quantum mechanical method. The initial steps of the nitrogen fixation process are discussed within the framework of the present model, and it is shown that of several binding sites, initial location of the nitrogen molecule inside the MoFe cofactor is favored. Possible pathways for electron and proton delivery to the active site are also suggested on the basis of electrostatic potential calculations.
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  • 4
    ISSN: 0947-6539
    Keywords: azadienes ; azepines ; cycloadditions ; Fischer carbenes complexes ; reaction mechanisms ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4-Amino-1-azadienes 1 react with α,β-unsaturated Fischer carbene complexes at -40°C to give stereoselectively a variety of substituted 3H-4,5-dihydroazepines 3; similarly, 1-hydroxy-1-azadienes (α,β-unsaturated oximes) 6 afforded the corresponding azepine derivatives 7. Chiral, nonracemic carbene complexes 11 gave azepines 12-13 (d.e. = 40-44%) upon reaction with oxime 6a; the major isomers were obtained in a diastereomerically and enantiomerically pure form (45-50% overall yield) after crystallization. An X-ray structure of 12a allowed assignment of the absolute stereochemistry. The acid hydrolysis of azepines synthesized provided racemic and enantiomerically pure 1,6-dicarbonyl compounds (±)-5, (±)-9, and (-)-14, as well as diol (-)-15. The mechanism of the reaction of 1 and 2 was investigated by multinuclear (1H, 13C, 15N, and 183W) NMR characterization of four intermediates (A, B, C, and D) at low temperature. The experimental sequence of events involves: i) 1,2-nucleophilic addition of the unsubstituted imine nitrogen of 1 to the metal carbene function (zwitterion A, -60°C), ii) cyclization to the seven-membered ring with 1,2-migration of the pentacarbonyl metal (zwitterion B, -40°C), iii) reductive elimination and coordination of the metal to the amine nitrogen (intermediate C, -40°C), and iv) thermal decomplexation and tautomerization (intermediate D and compound 3, above -20°C).
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    ISSN: 0947-6539
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 6
    ISSN: 0947-6539
    Keywords: bimetallic complexes ; NLO materials ; sandwich complexes ; sesquifulvalenes ; solvatochromism ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to construct bimetallic organometallic donor-acceptor complexes with nonlinear optical (NLO) properties, the bimetallic sesquifulvalene complexes [{CpFe(η5-C5H4)}Z{η7-C7H6)Cr-(CO)3}]BF4 (2BF4) have been synthesized with different bridging functions Z (2a: Z = - 2b: Z = C2; 2c: Z = (E)-C2H2). X-ray structure determinations show that 2a BF4 and 2c BF4 crystallize in acentric space groups (P41, P212121), whereas crystalline 2b BF4 has the centric space group P21/c. The organometallic fragments in 2a adopt a transoid conformation, those in 2b and 2c are cisoid. The cyclo-C5 and cyclo-C7 rings of the sesquifulvalene ligands are almost coplanar; this allows an optimum electronic interaction between the ferrocenyl donor and the [η7-C7H6)Cr(CO)3]+ acceptor moiety in the crystalline state. Cyclovoltammetric studies show an electrochemically reversible one-electron oxidation ( 〉 0 mV vs. FeH/FcH+, FcH = ferrocene) and an irreversible one-electron reduction (≤-900 mV), which are assigned to the ferrocenyl and [(η7-C7H6)Cr(CO)3]+ units, respectively. UV/vis spectra reveal low-energy absorptions for 2a-c at about λ=600 nm, showing strong negative solvatochromism. These absorption maxima are related to a charge-transfer excitation between the ferrocenyl and the [(η7-C7H6)Cr(CO)3]+ groups, indicating considerable nonlinear optical properties. Determination of the first hyperpolarizability β by means of hyper Rayleigh scattering yields exceptionally large β values: β(2b) = 570 × 10-30 esu and β(2c) = 320 × 10-30 esu. These unexpectedly large β values are explained by resonance enhancement.
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  • 7
    ISSN: 0947-6539
    Keywords: azo dyes ; circular dichroism ; data fitting ; formation constants ; protein complexation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Difference absorbance and circular dichroism techniques show that two complexes are formed between human serum albumin (HSA) and Methyl Orange (MO). The stoichiometries of the two HSA-MO complexes (1:1 (C1) and 1:2 (C2)), their association constants (K1, 1 = 2.32 (0.18) × 105 M-1 and K1, 2 = 1.12 (0.15) × 1011 M-2), and both absorbance and dichroic spectra have been determined by a computational approach. Nearly 900 experimental points, consisting of absorbance and CD measurements registered in the 340-550 nm interval and over a wide range of concentrations of protein and ligand, have been included in a unique fitting procedure. The Scatchard plot indicates the existence of a unique binding site which can accommodate up to two molecules of MO in a positive co-operative process. Calculation of the CD spectrum for the C2 complex according to the DeVoe method reproduces the fitted dichroic spectrum for the same complex. The shapes of the fitted absorbance and dichroic spectra, as well as the influence of concentrated NaCl or ethylene glycol on the absorbances of both free MO and HSA-MO mixtures are consistent with the presence of dominant electrostatic interactions in C1. The C2 complex can be envisaged as a unique chromophore, consisting of two MO units associated in a stacking process into the same binding site of HSA, leading to a well-defined chirality. The general validity of this multitechnique, multiwavelength approach in the investigation of protein-ligand complexes is discussed.
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  • 8
    ISSN: 0947-6539
    Keywords: catalysis ; crystal structure ; oxidations ; rhenium peroxo complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rhenium oxides Re2O7 and ReO3 react with hydrogen peroxide solutions yielding peroxo complexes that efficiently catalyze the oxidation of olefins, aromatics, and certain organometallic compounds. In contrast, related oxides of molybdenum (MoO3) and vanadium (V2O5) do not activate H2O2 under comparable conditions. The active rhenium peroxo complex was isolated from the system Re2O7/H2O2: the crystalline red-orange, explosive compound of formula H4Re2O13 is the most oxygen rich rhenium compound isolated to date. Its structure resembles a “peroxo perrhenic acid”. The binuclear compound could be isolated in the form of a diglyme adduct, structurally defined as two corner-sharing pentagonal bipyramids with apical oxo and aquo ligands; the equatorial positions are occupied by the bridging oxygen and by n2-peroxo groups (two [O2]2- ligands per rhenium). In contrast to the known complex [CH3ReO(O2)2].H2O, the new peroxo species [O{ReO(O2)2.H2O}2] decomposes hydrolytically during the catalytic cycle and can thus not compete in terms of catalytic activity in oxidation reactions involving H2O2. Hydrolysis yields “perrhenic acid” Re2O7.2H2O, the diglyme adduct of which compound was also characterized by means of an X-ray diffraction analysis.
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  • 9
    ISSN: 0947-6539
    Keywords: asymmetric syntheses ; chromium complexes ; diones ; oxy-Cope rearrangements ; polycycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The tricarbonylchromium complex 3 of 1,2-dioxobenzocyclobutene (1) is easily prepared by hydrolysis of diacetal 4. Complex 3 stereoselectively undergoes both single and double nucleophilic addition reactions at the keto groups. As a consequence, addition of excess alkenyllithium to 3 gives rise to a dianionic oxy-Cope rearrangement yielding benzocyclooctenedione complexes with good diastereoselectivity. Trapping of the bis(enolate) intermediate with chlorotrimethylsilane gives bis(enolether) 23. Subsequent addition of two different alkenyllithium derivatives yields the asymmetrically substituted rearrangement product 15. To some extent, dependent on the method of hydrolysis, an intramolecular aldol addition follows the dianionic oxy-Cope rearrangement. This results in the formation of benzoanellated bicyclo[3.3.0]octane derivatives and, in the case of 1-cyclopentenyllithium as the alkenylmetal, in the tetraquinane system 19. The trans-anellation of one of the cyclopentane rings in trans-20 has been verified by an X-ray structural analysis. The highly substituted rearrangement product 21/22 is formed only in small yield; in solution the bis(enol) tautomeric form 22 is favored over diketone 21.
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  • 10
    ISSN: 0947-6539
    Keywords: eliminations ; orbital interactions ; solvent effects ; substitutions ; theoretical chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The model reaction system F- +C2H5F + nHF (n = 0-4) has been investigated by use of a density-functional method, in order to achieve a qualitative understanding of the effect of solvation on the E2 and SN2 reactions. Two characteristic effects already occur upon monosolvation: a) the activation energies of the E2 and SN2 pathways increase significantly and even become positive, because reactants are more strongly solvated than transition states; b) the SN2 transition state is stabilized much more and becomes lower in energy than the anti-E2 transition state. This agrees with general experience from gas- and condensed-phase experiments. The solvation is analyzed from two complementary viewpoints: a) as an interaction between solvent molecules and the F-/C2H5F reaction system; b) as an interaction between the [F-, nHF] solvated base and the C2H5F substrate. The extent to which condensed-phase characteristics can be modeled by this microsolvation approach is discussed.
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  • 11
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. cpi 
    ISSN: 0947-6539
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 12
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    ISSN: 0947-6539
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 13
    ISSN: 0947-6539
    Keywords: cyclic compounds ; medium-sized ; rings ; tetraketones ; transannular interactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By using a fast-mixing nozzle in a Fourier transform microwave spectrometer, any chemical reaction accompanying mixing of H2S and BrCl was prevented, thus allowing the observation of the pre-reactive complex H2S ··· BrCl. The rotational spectra of eight isotopomers of the complex were recorded. The analysis of the determined spectroscopic constants shows that the atoms S ··· Br—Cl are collinear or nearly so and that the H2S plane is approximately perpendicular to the S ··· Br—Cl axis with r(S ··· Br) = 3.094 (7) Å. This geometry is in agreement with previously stated rules for B ··· XY complexes, where B is a Lewis base and XY is an (inter)halogen molecule. The intermolecular interaction is shown to be relatively weak, both in terms of the intermolecular stretching force constant kσ and the intramolecular electric change redistribution δ within the BrCl subunit that accompanies formation of H2S ··· BrCl.
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  • 14
    ISSN: 0947-6539
    Keywords: carbonyl oxides ; dioxiranes ; mechanistic studies ; oxidations ; thianthrene 5-oxide ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thianthrene 5-oxide (SSO) constitutes a useful mechanistic tool for the assessment of the electronic character of oxygen transfer agents by means of their Xso values, which reflect the extent of nucleophilic oxidation at the SO site in SSO. Treatment of dioxiranes 1 a-d with the SSO probe confirms that these are electrophilic oxidants (Xso 〈 0.15). Dioxirane sulfoxidation is sensitive to protic solvents and acids, which implies a polar mechanism (SN2) with nucleophilic attack of the sulfide electron pair on the dioxirane peroxide bond. In contrast, the carbonyl oxides 2 a and b, diethyl persulfoxide (3), and adamantylideneadamantane perepoxide (4) are nucleophilic oxidants (Xso 〉 0.85). However, the cyclopentadienone carbonyl oxides 2 c and d show low Xso values typical for electrophilic oxygen transfer agents. For these carbonyl oxides, photoisomerization to the respective dioxiranes is proposed under the photooxidation conditions of the diazoalkanes. Additionally, the trans/cis ratio of bissulfoxides (SOSO) formed provides valuable information on the stereochemical course of the oxygen-transfer process due to the steric requirements of the oxidant. Thus, the electrophilic dioxiranes preferentially attack the axial lone pair of SSO because of repulsion by the peri hydrogen atoms to afford trans-SO-SO.
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  • 15
    ISSN: 0947-6539
    Keywords: conformational analysis ; galabioside ; hydrogen bonds ; protein recognition ; thioglycosides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The two thio analogues (2 and 3) of TMSEt galabioside [2-(trimethylsilyl)ethyl 4-O-(α-D-galactopyranosyl)-β-D-galactopyranoside, 1], having anomeric sulfur instead of anomeric oxygen atoms, were synthesized and their conformations investigated by NMR and computational (MM 3) methods. A spacer galabioside was covalently coupled to aminated microtiter plates, and binding of a bacterial pilus adhesin (PapG) to the plates was inhibited by the soluble ligands 1, 2 and 3. The ligand 2, which has an intersaccharidic sulfur linkage, was a much less efficient inhibitor than 1, which has the natural oxygen linkage. The inhibitory power of ligand 3 was only slightly less than that of 1. An NMR experiment with 1 and 2, in which hydroxyl-group hydrogens had been partially (50%) substituted by deuterium, demonstrated the presence (in 1) and absence (in 2) of an intramolecular (HO 2′ - HO 6) hydrogen bond. This result indicates that the conformations of 1 and 2 are different and that the difference is sufficient to cause the observed (≈ 30 times) reduction of the saccharide-protein binding strength.
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  • 16
    ISSN: 0947-6539
    Keywords: enzyme inhibitors ; niobium complexes ; peptide aldehydes ; pinacol coupling ; vanadium complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Peptide aldehydes 15 a-c are prepared without epimerization from enantiomerically pure (S)-α-amino acids (Scheme 3). Reductive pinacol homocoupling of 15 a-c, induced by vanadium complex 11 or niobium complex 16 in refluxing THF, yields C2-symmetrical (S,R,R,S)-configurated 6a, 6b and 2, respectively, with moderate to high stereoselectivity (Scheme 4). In a novel protocol for the preparation and utilization of THF solutions of 11, the isolation of air-sensitive intermediates can be avoided and the potent HIV protease inhibitor 2 prepared in enantio- and diastereomerically pure form on a kilogram scale without chromatographic purification. The (S,R,R,S) selectivity of the pinacol homocouplings is confirmed by means of an independent, stereochemically unequivocal synthesis of 6 a and 2 from D-mannitol 4 (Scheme 1).
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  • 17
    ISSN: 0947-6539
    Keywords: alkynes ; asymmetric syntheses ; cyclopropanes ; spiro compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A variety of chiral, nonracemic 2-alkoxy-1-alkynylcyclopropanes 7 were synthesized in good to very good yields from enantiomerically pure glycidol derivatives (glycidol tosylate, epichlorohydrin) by boron trifluoride promoted addition of lithium trimethylsilylacetylide followed by protection of the secondary hydroxyl group and finally a diastereoselective γ-elimination. The 2-ethoxy derivative (S,R)-7 b was deprotonated with n-butyllithium, and the resulting 1-lithio-2-ethoxy derivative (S,R)-20 functionalized by treatment with oxygen followed by tosyl chloride. Protodesilylation and catalytic hydrogenation smoothly furnished 1-ethenylcyclopropyl sulfonates, which underwent a clean Pd0-catalyzed SN2′-type substitution with dimethyl propargylsodiummalonate to give the (E)-configurated enyne (R,E)-26 with a methylenecyclopropane end group. A diastereoselective Pauson-Khand reaction completed the sequence to give the enantiomerically pure spirocyclopropaneannelated bicyclo[3.3.0]octane derivative 31.
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  • 18
    ISSN: 0947-6539
    Keywords: clusters ; gas-phase chemistry ; ionmolecule reactions ; iron complexes ; mass spectrometry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We report on the gas phase reactions of small Fe+n clusters (n = 2-10) with O2, N2O and CO2 in an FT-ICR mass spectrometer. Under our experimental conditions, clusters of all sizes reacted readily with O2 and all but the dimer reacted with N2O. Only the smallest Fe+n clusters (n = 2-4) appeared to activate CO2. For all X-O molecules (X = O, N2, CO), reaction pathways were observed that include the transfer of O atoms. In addition, the reactions with O2 and N2O were accompanied by the loss of one or two Fe atoms. Thermochemical considerations based upon the well-known X-O bond energies were used to calculate Fen-O+ bond dissociation energies (BDEs) for sizes n = 2-6; these amount to roughly 550 kJ mol-1 and thus are considerably higher than the BDE of the Fe-O+ ion. All oxidation reactions of the Fe+n clusters (n = 2-6) studied in more detail were terminated by products of FexOx+ stoichiometry (x = 1-4). These “microoxides of iron” are not able to activate any further X-O bonds. Secondary reactions of FexOx+ clusters with C6H6, C2H4 and NH3 were investigated for two selected sizes (x = 2, 3) and compared with reactions of the naked Fe+n clusters.
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  • 19
    ISSN: 0947-6539
    Keywords: alkyne complexes ; carbon-carbon coupling ; pentaenes ; rhodium complexes ; vinylidene complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of [Rh(η3-C3H5)-(PiPr3)2] (1) with HC≡C—CH(Ph)OH yields the alkynyl(vinylidene) complex trans-[Rh{C≡C—CH(Ph)OH}{=C=CH-CH(Ph)OH}(PiPr3)2] (2), while from 1 and HC≡C—CPh2OH the alkynyl-(enyne)metal derivative trans-[Rh(C≡C—CPh2OH){n2-(E)-Ph2(OH)C—C≡C—CH=CH-CPh2OH} (PiPr3)2] (3) is obtained. On treatment with 1-alkyn-3-ols HC≡C—CR2OH (R = Me, Ph, iPr), the highly reactive π-benzyl compound [Rh(n3-CH2Ph)(PiPr3)2] (4) yields the five-coordinate complexes [RhH(C≡C—CR2OH)2(PiPr3)2] (5-7) of which those with R = Me and Ph can be converted to the alkynyl(vinylidene)metal isomers trans-[Rh(C≡C—CR2OH)(=C=CH-CR2OH)-(PiPr3)2] (8, 9). Compounds 8 and 9 react with L′ = CO and isocyanides by migration of the alkynyl ligand to the vinylidene unit to give the enynylrhodium(I) complexes trans-[Rh{n1-(Z)-C(C≡C—CR2—OH)=CH-CR2OH}(L′)(PiPr3)2] (10, 11: L′ = CO; 12-15: L′ = CNR′). Cleavage of the Rh-C s̰-bond of 10 with CF3-CO2H affords trans-[Rh(n1-O2CCF3)-(CO)(PiPr3)2] (16) and the enyne (E)-Me2(OH)C—C≡C—CH=CH-CMe2OH (17). Compounds 5-7 react with L′ = CO and isocyanides to give the octahedral 1:1 adducts [RhH(C≡C—CR2OH)2(L′)(P-iPr3)2] (18-20 and 24-27), of which the CO derivatives 18-20 readily eliminate HC≡C—CR2OH to yield trans-[Rh-(C≡C—CR2OH)(CO)(PiPr3)2] (21-23). On treatment of 6 or 9 (R = Ph) with Al2O3 in the presence of chloride ions, besides trans-[RhCl(=C=C=CPh2)(P-iPr3)2] (28) the hexapentaenerhodium(I) complex trans-[RhCl(n2-Ph2C=C=C=C=C=CPh2)(PiPr3)2] (29) is formed. The kinetically preferred isomer trans-[RhCl(n2-Ph2C=C=C=C=C=CPh2)(P-iPr3)2] (33) has been prepared from [RhCl(PiPr3)2]2 and Ph2C=C=C=C=C=CPh2; it rearranges smoothly at room temperature to the thermodynamically more stable isomer 29. The molecular structures of 7 and 29 have been determined.
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  • 20
    ISSN: 0947-6539
    Keywords: charge transfer complexes ; diimine complexes ; emission spectroscopy ; manganese complexes ; zeolites ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Manganese complexes of 2,2′-bipyridine (bpy) and 1,10-phenantroline (phen) have been synthesised in the supercages of cubic NaX and NaY and in the hypercages of the hexagonal NaEMT faujasites. The coordination and redox chemistry were studied with ESCA, CA, FT-IR, FT-Raman, diffuse reflectance and emission techniques. FT-IR/FT-Raman shows cis coordination for all complexes and a high Mn-N stretching frequency in the phen complexes as a result of steric constraints imposed by the ligand. [Mn(bpy)2]2+ in the different zeolites shows metal-to-ligand charge transfer (MLCT; at 495 nm); for [Mn(phen)2]2+-NaY the MLCt is broadened owing to complex distortion. On MLCT excitation [Mn(bpy)2]2+ complexes show an ipsochromic shift in the emission and an increase in quantum yield with increasing steric restrictions imposed by the zeolite. The ipsochromic shift of the emission band of [Mn(phen)2]2+ in NaY results from the combined effect of the ligand field (this suggests emission from a CT state) and of coordinative distortion. The key factor influencing the emission properties is found to be the overall matrix-induced complex distortion. Cation stabilisation of the ligand anion affects emission indirectly. The decay times for [Mn-(bpy)2]2+-NaY are in the millisecond range (7.5-11.5 ms). A proposed model for excitation and emission properties of zeolite-occluded MnII complexes involves excitation of a quartet CT state, intersystem crossing and subsequent emission. The enhanced stability of the coordination sphere in the zeolite allows complexes to luminesce from a CT state, which is not detected in solution. The zeolite behaves as a supramolecular cryptating agent, protecting complexes from photodissociation.
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  • 21
    ISSN: 0947-6539
    Keywords: barbiturates ; macrocycles ; molecular recognition ; receptors ; zinc complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new bis-zinc(II) receptor (Zn2L), which has two macrocyclic 12-membered tetraamine (cyclen) ZnII complexes connected through a p-xylene bridge, has been synthesized as a novel host molecule to recognize barbiturates (such as barbital (bar)) in aqueous solution. Each of the zinc(II) ions in the biszinc(II) receptor was originally intended to match the dianionic barbital anion (bar2-) with supplementary hydrogen bonds between the cyclen NH's and the three carbonyl oxygens in complementary positions to yield a 1:1 complex, Zn2L-bar2-. From an aqueous solution of equimolar Zn2L and barbital at pH 8, however, a cyclic 2:2 complex, (Zn2L-bar2-)2, was isolated and characterized by X-ray crystal analysis. The NMR study in 10% (v/v) D2O/H2O has revealed dissociation of (Zn2L-bar2-)2 solely into the original target 1:1 complex Zn2L-bar2- and established the dimerization constant for 2Zn2L-bar2- → (Zn2L-bar2-)2, Kd ( = [(Zn2L-bar2-)2]/[Zn2L-bar2-]2) to be 103.4 M-1. The thermodynamic parameters were evaluated from the NMR measurements at 25, 35, 45, and 55°C: ΔG = -1.9 × 104 J mol-1, ΔH = - 3.3 × 104 J mol-1, ΔS = - 49 J mol-1 K-1 at 25°C. Potentiometric pH titration of Zn2L (1 mM) and barbital (1 mM) disclosed extremely facile deprotonation of the two imido groups of barbital at pH less than 7 to form the dianionic barbital-bound ZnII complexes Zn2L-bar2- and (Zn2L-bar2-)2, where-by the barbital binding affinity for Zn2L was estimated to be Kbar ( = [Zn2L-bar2-]/[uncomplexed Zn2L][uncomplexed barbital]) = 105.8 M-1 at pH 8 and 25°C with I = 0.10 (NaNO3). The significance of the bis-zinc(II) receptor in stabilizing the dianionic barbital is evident by comparison with the interaction of ZnII-cyclen complex (ZnL) with barbital, which yields only a 1:1 monoanionic barbital complex, ZnL-bar- (Kbar = [ZnL-bar-]/[uncomplexed ZnL][uncomplexed barbital] = 104.2M-1 at pH 8 and 25°C with I = 0.10 (NaNO3)).
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  • 22
    ISSN: 0947-6539
    Keywords: binding assays ; immunosensors ; electrochemical polymerisations ; peptide derivatives ; peptide immobilisation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For the first time, antigenic peptides have been immobilised by electrochemical polymerisation after having been modified with a polymerisable functional group. 3-Hydroxyphenylacetic acid was chosen as the novel polymerisable group. The synthetic peptides represent epitopes of the bovine foot and mouth disease virus and of the sodium channel of the cardiac muscle. The polymerisation was performed by applying a constant anodic potential or by cyclic voltammetry. A combination of these two methods was also employed, that is, cyclic voltammetry with a delay at the anodic vertex potential. No additional free phenolic monomer was required for the polymerisation. The layers formed by the polymerisation were recognised by specific antibodies. The specific binding of the antibodies to the polymer film could be demonstrated by ELISA, an enzyme-linked amperometric immunoassay, and electrochemical impedance measurements, as well as by fluorescence-labelled antibodies. A peptide derived from laminine was also immobilised by electrochemical polymerisation. It could be shown that neuroblastoma cells adhere to this layer.
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  • 23
    ISSN: 0947-6539
    Keywords: amino alcohols ; asymmetric syntheses ; dihydroxylations ; diol cleavage Horner-Wittig reaction ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Spiroepoxide 1 was prepared from quinidine and converted into β-amino alcohol 3 (86% over two steps). Dihydroxylation of enantiopure oxazatricylic olefin (E)-4 provided diastereomeric diols 5a and 5b. Stereospecific conversion of 1,2-secondary, tertiary diol 5b into tetracyclic spiroepoxide 6 was accomplished in high yield by a one-pot tosylation-cyclization procedure. 1,2-Diol cleavage with NaIO4 in 80% acetic acid afforded the new tricyclic dehydrorubanone 7, containing the 4-oxa-7-azatricyclo[4.3.1.03,7]-decan-2-one core structure. Similarly, acetylated rubanone 9 was prepared on a 20 g scale. Reduction with NaBH4 in the presence of CeCl3 provided rubanols 10a and 10b (1:1.1). Horner-Wittig reaction of 9 with diethyl cyanomethylphosphonate was (Z)-selective, furnishing unsaturated nitrile (Z)-13. Conversion into the α,β-unsaturated aldehyde (Z)-14 and reduction afforded enartiopure allylic alcohol (Z)-12, which is a new isomer of the key quinidine metabolite 15.
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  • 24
    ISSN: 0947-6539
    Keywords: crystal structure ; density functional calculations ; polyarsenido complexes ; polyphosphido complexes ; Zintl anions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Zintl anion P3-7 reacts with complexes of transition metal halides to form multinuclear metal phosphorus clusters. Reaction of Li3P7·3 DME with [FeCp(CO)2Br] or [NiCl2(PBu3)2] leads to the formation of [P7{FeCp(CO)2}3] (1) and [{Ni(PBu3)2}4P14] (2), respectively. X-ray structure determinations show that in 1 the P7 cage of Li3P7 remains intact but in 2 a P14 framework is formed by linkage of two norbornadiene-like P7 units. The P14 skeleton coordinates to four Ni(PBu3)2 groups. LiCp* and CoCl2 react with P7(SiMe3)3 to give [(Cp*Co)3-(P2)3] (3) with three Cp*Co groups bridged by P2 units. Reaction of FeCl2 and LiCp* with P7(SiMe3)3 yields [(Cp*Fe)3P6][FeCl3(thf)] (4) or [(Cp*Fe)3{n3-P3)Fe}P6] (5), depending on the reaction conditions. In 4 the structure of the Fe3P6 core of the [(Cp*Fe)3P6]+ cation is comparable to closo-B9H92-, while in 5 the Fe4P6 core does not obey the Wade rules. The unusual Co-As cluster [Co6As12(PEt2Ph)6] (6), prepared from K, As, and [CoCl2(PEt2-Ph)2], can be described as a Co6As6 heteroicosahedron linked to two Co3As3 octahedra by common Co3 faces. A theoretical treatment within the density functional approximation reproduces the experimental structures of 2 and 6 and allows an interpretation of molecular electronic structures. In 2 one finds P-P double bonds that are delocalized to some extent into vacant Ni AOs. For the cage compound 6 the Co 3 d AOs participate in cage bonding and 38 electrons can be assigned to cage bonds; this is in accord with the (2N + 2) rule for 18-atom cages but not with the usual electron counting rules.
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  • 25
    ISSN: 0947-6539
    Keywords: biomineralization ; medium-sized rings ; calcite ; crystal morphology ; glycoproteins ; polysaccharides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of 4,4,9,9-tetramethyl-1-oxa-cycloundecane-5,6,7,8-tetrone (9) and 5,5,10,10-tetramethyl-1-oxa-cyclotridecane-6,7,8,9-tetrone (10) has been achieved in a multistep procedure. The key steps in this synthesis were the ring closure of 23 and 24 to 25 and 26, respectively, and the oxidation of the triple bond with RuO2/NaIO4 to the dihydroxydiketones 31 and 32. Compound 9 is the first cyclic tetraketone for which an intramolecular donor-acceptor stabilization has been found. A strong transannular interaction between the ether oxygen and the C4O4 unit in 9 was detected by X-ray studies on single crystals of 9. The transannular distance is 2.7-2.8 Å. Further evidence for a strong transannular interaction was obtained from the comparison of the reduction potential and the first band in the UV/Vis spectrum with the corresponding values from other openchain tetraketones. These findings were substantiated by PE investigations on 9. The crystal structures of the dihydroxy-diketones 31 a and 32 a showed that, in the case of the eleven-membered ring (31 a), there are also short transannular distances between the ether oxygen and the C2O2 moiety (2.5 Å and 2.9 Å). In the case of the thirteen-membered ring (32 a), no transannular interactions were found in the solid state.
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  • 26
    ISSN: 0947-6539
    Keywords: computer simulations ; high-pressure chemistry ; lanthanide complexes ; ligand exchange ; mechanistic studies ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We studied the microscopic mechanisms of the water exchange reaction between the hydration shells of lanthanide(III) ions (Ln = Nd, Sm, Yb) and bulk water by means of molecular dynamics simulations. In contrast to the residence time of a water molecule in the first hydration shell (τres (1st shell) = 1577, 170 and 410 ps for Nd3+, Sm3+ and Yb3+, respectively), that in the second hydration shell is nearly independent of the type of the cation and amounts to 12-18 ps. Along the lanthanide series a change in the coordination number from 9 to 8 is coupled to a changeover in the water exchange mechanism. The observed water exchange events on the [Nd(H2O)9]3+ aqua ion follow a dissociatively activated Id mechanism via an eightfold-coordinated transition state of square antiprismatic geometry. The lifetime of the transitory square antiprism varies between virtually 0 and 10 ps. The assignment of an Id mechanism (instead of a limiting D mechanism) is supported by the existence of a preferential arrangement between the exchanging water molecules (1800) and by the fact that the calculated average activation volume ΔV≠ = + 4.5 cm3 mol-1 is clearly smaller than the estimated activation volume ΔV≠lim ≈ΔV0 = + 7.2 cm3 mol-1 for a limiting D process. In the case of Sm3+ a ninth water molecule exchanges frequently between the first hydration shell and the bulk and maintains the coordination equilibrium between a [Sm(H2O)8]3+ and a [Sm(H2O)9]3+ aqua ion. The resulting trajectory pattern of incoming and leaving water molecules is an alternation of elimination and addition reactions and cannot be classified into the scheme of D, I or A mechanisms for substitution processes. The reaction volume ΔV0 for the coordination equilibrium [Sm(H2O)8]3+ + H2O → [Sm(H2O)9]3+ can be evaluated consistently both by a thermodynamic and a geometric approach. The observed exchange events for [Yb(H2O)8]3+ exhibit the characteristics of an Ia mechanism. The water exchange takes place via a transition-state geometry close to that of a tricapped trigonal prism and involves a slightly negative activation volume.
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  • 27
    ISSN: 0947-6539
    Keywords: ab initio calculations ; dihydrogen complexes ; isotope effects ; NMR spectroscopy ; osmium complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of complex [OsHCl-(CO)(PiPr3)2] (1) with hydrogen gives the trans-hydridodihydrogen complex [OsH-Cl(n2-H2)(CO)(PiPr3)2] (2). The H-H distance in the dihydrogen ligand, determined by variable-temperature 1H T1 measurements, is 0.8 Å. The fast-spinning nature of the dihydrogen ligand of 2 has been deduced by evaluating the deuterium quadrupole coupling constant for the n2-D2 ligand of [OsDCl(n2-D2)(CO)(PiPr3)2] ([D3]2). Measurements of the equilibrium constants for formation of 2 (K) give ΔH0 = - 14.1 ± 0.5 kcal mol-1 and ΔS0 = - 30 ±1 e.u. An equilibrium isotope effect Kd/K of 2.8 is found for this reaction. The activation parameters for the H2 loss from 2 are ΔH
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  • 28
    ISSN: 0947-6539
    Keywords: cyclohexenols ; elimination reactions ; gas-phase chemistry ; mechanistic studies ; nucleophilic substitutions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Our radiolytic study of the occurrence in the gas phase of concerted SN2′ reactions on several open-chain allylic oxonium ions generated in the gas phase from the attack of gaseous GA+ acids (GA+=CnH+5 (n = 1, 2), iC3H+7, and (CH3)2F+) on suitable substrates is now continued with cyclic allylic alcohols, such as 3-methyl-2-cyclohexen-1-ol (1) and 1-methyl-2-cyclohexen-1-ol (2), with both MeOH and NMe3 as neutral nucleophiles. With MeOH as the nucleophile, the substitution reaction exclusively takes place on 1 as the starting compounds, whereas when the substrate is 2 it is accompanied by extensive elimination. With NMe3, only the elimination reaction is observed in the same systems. The analysis of the isomeric distribution of the substitution and elimination products allows definition of the corresponding reaction patterns. As for open-chain oxonium ions, the nucleophilic attack on O-protonated 1 and 2 is preceded by significant intramolecular interconversion. Partial unimolecular dissociation of the same ionic intermediates also takes place. After careful evaluation of the extent of these side processes, it is demonstrated that the O-protonated 1 undergoes the concerted SN2 process with MeOH almost exclusively (≥ 99%). With O-protonated 2, how ever, the concerted SN2′ pathway (84-95%) prevails over the classical SN2 one (6-17%). Concomitant [1,2] (E2) and [1,4] elimination (E2′) pathways involve attack of the selected nucleophiles on the oxonium ions from 1 and 2. Their relative extent (E2′/E2:1.78-1.96 (1); 1.43-1 70 (2)) appears only slightly dependent on the nature of the ionic substrate, the nucleophile (whether MeOH or NMe3), and the leaving group (whether H2O or MeOH). The effects of both intrinsic structural factors and experimental conditions in determining the SN2′/SN2 and E2′/E2 branchings in the selected oxonium ions is discussed and compared with related gas-phase data.
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  • 29
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    ISSN: 0947-6539
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 30
    ISSN: 0947-6539
    Keywords: asymmetric synthesis ; chirality ; enolates ; hydrogen bonds ; structure elucidation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of acetophenone with tetrabutylammonium hydroxide affords the tetrabutylammonium enolate of phenyl (2-hydroxy-2-phenyl)propyl ketone. The crystal structure of this chiral enolate shows intramolecular hydrogen bonding between the hydroxyl group and the enolate oxygen atom. Furthermore, the α-methylene units of the ammonium counterion form hydrogen bonds to the basic enolate C and O atoms and to the O atom of the hydroxy group. This three-point bonding occurs selectively on the Re,Re side, a phenomenon which may be responsible for the direction of diastereo-selectivity in the epoxide-forming reaction of the enolate with N-bromosuccinimide.
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  • 31
    ISSN: 0947-6539
    Keywords: crystal structure ; cyclodextrins ; dansyl derivatives ; fluorescent sensors ; self-inclusion ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A monofunctionalized β-cyclodextrin containing a dansyl moiety, 6- deoxy- 6 - N - ( N′- (5- dimethylamino - 1 - naphthalenesulfonyl)diaminoethane) - β-cyclodextrin (CD-en-DNS, 2), was synthesized and its crystal structure determined. It was shown that the dansyl group is fully encapsulated within the cyclodextrin cavity, with the dimethylamino and sulfonyl groups emerging from opposite sides. The shape of the cavity is considerably flattened, since O(4)-O(4) distances parallel to the naphtalene ring were found to be longer than the others. The conformation of the diaminoethane linker was found to be determined by the inclusion of the dansyl group and by a hydrogen bond between the sulfonamide NH and one of the O(6)-H groups on the cyclodextrin rim. The self-inclusion features of the aromatic moiety were found to be consistent with the solution data: 1H NMR ROESY spectra suggested that the orientation of the dansyl moiety observed in the solid state was retained in aqueous solution; the circular dichroism spectrum was consistent with an axial complexation model. Fluorescence spectra showed that the inclusion of the dansyl group in the cyclodextrin cavity considerably increases the quantum yield: time-resolved fluorescence experiments showed the presence of a long-lifetime component (16.1 ns), which was attributed to the included fluorophore. The ability of 2 to act as a fluorescence sensor was evaluated by the addition of several guests of different shape: fluorescence intensity was lowered, especially upon addition of adamantanecarboxylic acid. All the data obtained were consistent with the model of the in-out movement of the dansyl group from the self-included conformation observed in the solid state to a position more exposed to the bulk solvent. Copper(II) was shown to enhance the difference in the fluorescence of 2 in the presence of guests by additional static quenching.
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  • 32
    ISSN: 0947-6539
    Keywords: carbon-carbon coupling ; carbonyl complexes ; hafnium complexes ; ketenylidene complexes ; zirconium complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The biscyclopentadienyldicarbonyl derivatives of zirconium(II) and hafnium(II) ([MCp2(CO)2]; M=Zr, Hf) promote the reductive coupling of coordinated carbon monoxide to give, in the presence of N,N-dialkylcarbamtes of the tetravalent metals [M(O2CNR2)4], the ketenylidene complexes [M3Cp2(μ2-CCO)-(μ3-O)(O2CNR2)6] (1 a: M=Zr, R=Et; 1 b: M=Zr, R=iPr; 2: M=Hf, R=iPr). The yields of the isolated zirconium complexes are as high as 60%, while that of the hafnium derivative is 40%. The X-ray crystal structure analysis of 1 b shows that it consists of trinuclear molecules, with the three zirconium atoms held together by the bidentate C2O ligand, by the tridentate bridging oxide and by the bidentate carbamato groups. Labelling experiments with [ZrCp2(13CO)2] show that the ketenylidene ligand originates from the coordinated CO groups. These ketenylidene complexes, which are rare examples of compounds containing a CCO but no CO ligand, are characterized by an intense IR band at about 2015 cm-1, associated with the bridging C2O ligand. The ketenylidene group of 1 b was readily removed and replaced by a bidentate μ-oxo ligand of the same hapticity by reaction with carbon dioxide or acetone or by thermal decomposition. The resulting product [Zr3Cp2(μ-O)(μ3-O)-(O2CNiPr2)6] (3) crystallizes in the same space group as 1 b and with similar cell constants and bond parameters.
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  • 33
    ISSN: 0947-6539
    Keywords: catalysis ; diazo compounds ; epoxidations ; sulfur ylides ; synthetic methods ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel, neutral catalytic cycle for the synthesis of epoxides from carbonyl compounds and diazo compounds using catalytic quantities of transition metal salts and sulfides has been developed. In this catalytic cycle, the diazo compound is decomposed by the transition metal salt to give a metallocarbene, and this is picked up by the sulfide to give a sulfur ylide, which then reacts with the aldehyde to give an epoxide and returns the sulfide back into the catalytic cycle. To obtain good yields of epoxides it is necessary to maintain a low concentration of the diazo compound (by slow addition), otherwise dimerisation of the diazo compound is the dominant reaction. Factors affecting the outcome of the reaction were studied. The reactions are relatively insensitive to solvent, but are sensitive to the structure of the sulfide, the metal salt and the concentration. Unhindered sulfides give good yields of epoxides with any metal salt, but with hindered sulfides higher yields are obtained with Cu(acac)2 than with Rh2(OAc)4. The yields of epoxides are sensitive to sulfide concentration especially when using substoichiometric amounts of sulfides. Higher concentration leads to faster rates of formation and subsequent reaction of the sulfur ylides, and consequently to higher yields. This novel catalytic cycle has also been applied to base-sensitive aldehydes. We found that our new catalytic cycle for epoxidation gives much improved yields of epoxides compared to those obtained by traditional sulfur ylide chemistry and is tolerant to a wide variety of sensitive functional groups. Ketones also participate in the catalytic cycle, although they give reduced yields of epoxides compared to aldehydes and require a slightly elevated temperature.
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  • 34
    ISSN: 0947-6539
    Keywords: allenes ; cycloadditions ; Diels-Alder reactions ; mechanistic studies ; radical cations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several novel electron-rich aryl-allenes have been synthesized, characterized, and used as dienophiles in the radical-cation-catalyzed cycloaddition with 1,2,3,4,5-pentamethylcyclopentadiene, which affords, in most cases, the Diels-Alder products in 5 min at 0°C with a high peri-, chemo-, facial, and stereoselectivity. In line with oxidation-potential considerations it is concluded that the electron-transfer-induced reaction proceeds along a [3 + 2] pathway by cycloaddition of the diene radical cation to a neutral allene with a rather short chain length. The low cycloaddition yields from some of the allenes are interpreted as evidence for a stepwise mechanism involving distonic radical cations as key intermediates. We discuss the tendency of the distonic radical cations to undergo ring closure to the Diels-Alder-product radical cations in terms of enthalpy considerations, which, we suggest, offer a novel criterion for the design of stepwise radical cation reactions.
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  • 35
    ISSN: 0947-6539
    Keywords: ab initio calculations ; rotamers ; stereoisomers ; sulfane oxides ; torsional potentials ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ab initio MO calculations (MP 2/6-311 G**//HF/6-311 G**) have been performed for several isomers (including rotamers) of Me2S3O and Me2S3O2. MeS(O)SSMe exists as five rotamers; the most stable form (1a) has a helical backbone CSSSC with S-S bond lengths of 206.0 (SIISII) and 212.4 pm (SIISII). The most stable rotamer of MeS-S(O)SMe (2a), is less stable than 1a by 10.7 kJ mol-1; it is of Cs, symmetry, while a rotamer of Cs symmetry (2b) is less stable than 2a by only 1.4 kJ mol-1. Both 2a and 2b are stabilized by O ⃛ H hydrogen bonds. The S-S bond lengths of 2a are 210.0 and 212.0 pm; the CSSSC chain is not helical (CSSS torsion angles 166.3 and -75.4°). The 1,3-dioxide MeS(O)-SS(O)Me (3) has two equivalent chiral centers and exists as diastereomers. The most stable isomer 3a (RR)/(SS) is of C2 symmetry with methyl groups trans to each other; the SO bonds form an angle of about 90°. The meso form 3b is less stable than 3a by 17.2 kJ mol-1 and the rotamers 3c and 3d are less stable by 25.6 kJ mol-1 and 28.4 kJ mol-1, respectively. The trisulfane-1.2-dioxide MeS(O)-S(O)SMe has two nonequivalent chiral centers and exists as five isomers. The most stable form, the (RS)/(SR) form 4a, is less stable than 3a by 21.4 kJ mol-1 and is characterized by SS bonds of 220.9 (SIIISIII) and 208.3 pm (SIIISII). The rotamer 4b is less stable by 5.9 kJ mol-1. The isomers 4c, 4d, and 4e are all of (SS)/(RR) configuration and are less stable than 4a by 6.3, 12.7, and 12.0 kJ mol-1. For comparison, ab initio MO calculations (HF/6-311 G*) for tBuS(O)SS(O)-tBu yielded two diastereomers of practically identically energy that both contain helical CSSSC backbones. The (RS) form is less stable than the (RR)/(SS) form by 1.8 kJ mol-1.
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  • 36
    ISSN: 0947-6539
    Keywords: catalysis ; colloids ; gold-palladium colloids ; HRTEM ; hydrogenations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Layered bimetallic gold-palladium colloids in the size range of 20-56 nm have been synthesized by the seed=growth method: gold seeds were convered by palladium layers of various thickness and vice vaers. The outer metal was coordinated by trisulfonated triphenylphosphine and sodium sulfanilate ligands to stabilize the bimetallic particles to such an extent that they could be isolated in the solid state. Owing to the hydrophilic ligand shell, redispersion in water was posible in any concentration. High-resolution transmission electronn microscopy and energy-dispersive X-ray analysis was used to characterized the colloids. Stabilized and nonstabilized gold-palladium and palladium-gold systems on a TiO2 support were used as heterogeneous catalysts for the hydrogenation of hex-2-yne to cis-hex-2-ene. Both the palladium-plated gold seeds and the gold-plated palladium particles showed considerably increased activities compared with the pure metals. The ligand shell seems not to influence the catalytic behavior because protected and unprotected colloids behave very similarly.
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  • 37
    ISSN: 0947-6539
    Keywords: cyclic voltammetry ; iron complexes ; redox systems ; structure elucidation ; sulfur ligands ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of protonation and alkylation at the sulfur donors in metal-sulfur complexes have been investigated by taking the specific example of [Fe(CO)(“NHS4”)] (1). The 18 valence electron (VE) complex 1 consists of a low-spin FeII center and the dithioether thiolato amine ligand “NHS4”2-- ( = 2,2′-bis(2-mercaptophenylthio)diethylamine(2-)). Complex 1 can be reversibly protonated at the two thiolato donors; this results in an increase in ν(CO) of 35 cm-1 after the first protonation and 45 cm-1 after the second. Alkylation of 1 with one or two equivalents of the oxonium salts R3OBF4 (R = Me, Et) yields [Fe(CO)(“NHS4”-R)]BF4 (R = Me: 4, Et: 5), [Fe(CO)(“NHS4” -R2)](BF4)2 (R = Me: 6, Et: 7), and the methyl ethyl derivative [Fe(CO)(“NHS4” -Me-Et)](BF4)2 (8). An increase in ν(CO) of 31-32 cm-1 is observed for each successive alkylation. Due to the C1 symmetry of 1, complexes 4, 5, and 8 are formed as 1 : 1 mixtures of two diastereomers, whereas 6 and 7 are present as only one stereoisomer. Acidic hydrolysis of 4, 6, and 7 liberates the corresponding ligands [“NHS4” -Rn](BF4)n (9-11; n = 1,2), which were isolated as the ammonium tetrafluoroborate salts. The molecular structure of 8a has been elucidated by X-ray structure analysis. This shows that the Fe-N and Fe-S bonds in the [FeNS4] core do not change after alkylation of the thiolato donors despite the Δν(CO) of ca. 60 cm-1 between 1 and 8, which indicates a distinct decrease in electron density at the Fe center. This decrease can be rationalized by increased π-acceptor character of the sulfur donors upon protonation or alkylation. The change in electron density at the [Fe(“NS4”)] core is further corroborated by cyclic voltammetry. For each successive protonation or alkylation of 1, the redox couple potentials shift by 600-800 mV. As a consequence, the diethyl derivative, for example, gives rise to reduced species (19 or 20 VE) which are not observed for 1. The implications of these results for the reduction of N2 within the coordination sphere of the FeMo cofactor of nitrogenases are discussed.
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  • 38
    ISSN: 0947-6539
    Keywords: iron complexes ; magnetic susceptibility ; Mössbauer spectroscopy ; phasetransitions ; spin crossover ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The iron(II) complex [Fe(bpp)2]-(CF3SO3)2 H2O (bpp = 2,6-bis(pyrazolyl-3-yl)pyridine) shows a thermal spin transition associated with a hysteresis of approximately 140 K width. The transition temperatures T1/2 (where the fraction of HS species γHS = 0.5) are 147 K and ≍285 K in the cooling and heating directions, respectively. The compound shows the LIESST and reverse-LIESST effects at low temperatures. The relaxation of the metastable HS states generated by LIESST was observed quantitatively at temperatures between 77.5 and 85 K by Mössbauer spectroscopy. Metastable HS states can also be generated by rapid cooling of the sample. The relaxation of the metastable HS states formed by thermal spin-state trapping was monitored at temperatures between 104 and 118 K by magnetic susceptibility measurements. The relaxation mechanisms of the HS states generated by LIESST and thermal spinstate trapping are completely different. We suggest that the HS → LS relaxation after thermal spin-state trapping is triggered by an additional structural phase transition of the system.
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  • 39
    ISSN: 0947-6539
    Keywords: allylations ; allylsilanes ; double stereodifferentiation ; ephedrine ; homoallylic alcohols ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Enantiopure homoallylic alcohols 5, which are important building blocks in organic synthesis, are obtained with an ee of greater than 99% and a yield of 75-95% by cleavage of the secondary homoallylic ethers 4 using sodium in liquid ammonia. The ethers 4 are formed with excellent diastereoselectivity and in 52-89% yield by treatment of the aldehydes 1 with the trimethylsilyl ether of N-trifluoroacetylnorpseudoephedrine (2) in the presence of a catalytic amount of TMS triflate or TMS borontriflate, followed by addition of allylsilane 3. Nearly all achiral aliphatic aldehydes employed gave a diastereoselectivity of over 99:1. With the chiral aldehydes 24, the difference between matched and mismatched pairs was low; this reveals that there is strong reagent control.
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  • 40
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. cpi 
    ISSN: 0947-6539
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 41
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    ISSN: 0947-6539
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 42
    ISSN: 0947-6539
    Keywords: conformation ; crystal structure ; molecular modeling ; NMR spectroscopy ; sulfonamido-pseudopeptides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational preferences of chiral vinylogous aminosulfonic acids (vs-amino acids) and of the corresponding oligomers (vs-peptides) were investigated by a combination of X-ray crystallography, variable-temperature (VT) 1H NMR spectroscopy, FT-IR spectroscopy, and NOE experiments. The major source of conformational freedom in the monomers is the rotation around the C—C bond connecting the double bond with the allylic stereocenter (N—C*—C=C). The allylic conformational perferences can be altered in the oligomers by the formation of secondary structures enforced by hydrogen bonding. Twelve-membered-ring hydrogen bonding is detected in the crystal structure of vs-dipeptide 9, while fourteen-membered-ring bydrogen bonding is the most common folding pattern for the oligomers in chloroform solution. The experimental results are complemented by computer modeling: suitable force-field (FF) parameters for the unsaturated sulfonamide group nwere develiped from ab initio calculations. A Goodman-Still systematic pseudo-Monte-Carlo search was used for the conformational search. The conformers were minimized in chloroform with the GB/SA model. The calculations correctly predicted both the size of the hydrogen-bonded ring and its relative importance, in agreement with the experimental data in solution.
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  • 43
    ISSN: 0947-6539
    Keywords: chemoselectivity ; cinchona alkaloids ; clathrates ; osmium tetroxide ; spiro compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydrobromination of quinidine (1) with fuming HBr furnished diastereomeric secondary bromides 2a and 2b in 82% yield. After acetylation the resulting bromides 2a-Ac and 2b-Ac could be separated na dconverted stereospecifically into ethylidene rubanes Z)-4 and (E)-4, respectively. cis-Dihydroxylation of (Z)-olefin 4 with OsO4 was shown to be feasible by two catalytic variants, giving the two diastereomeric diols 5a and 5b, separable by chromatography. A simple onepot procedure was developed for converting the sterically hindered 1,2-secondary, tertiary diols stereospecifically into spiroepoxides (5a 6a-Ac; 5b 6b-Ac). Our procedure involves overall inversion of configuration. The procedure complements the Kolb-Sharpless route to epoxides from 1,2-disecondary diols with overall retention of configuration. The other two diastereomeric spiroepoxides 6c and 6d were prepared in one pot under different conditions (chloramine T, then alkali). Two unprecedented tricyclic allylic N,O-acetals (Z)-7 and (E)-7 were also obtained. The structure of spiroepoxide 6c (as a CH2Cl2 monosolvate) and of tricyclic olefinic N,O-acetal (E)-7 was corroborated by X-ray crystallography.
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  • 44
    ISSN: 0947-6539
    Keywords: copper complexes ; imidazole ligands ; redox systems ; structure elucidation ; enzyme models ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The new diimidazole ligand, bis (1-methyl-4,5-diphenylimidazol-2-yl)ke-tone (BIMDPK), has been synthesised, characterised and shown to form four-coordinate bis(diimidazole) CuII and CuI complexes in the salts [Cu(bimdpk)2]-[BF4]2 and [Cu(bimdpk)2][PF6], the structures of which have been determined by X-ray crystallography. The cations of these salts have a very similar geometry with CuII-Nav = 1.949 and CuI-Nav = 1.999 Å; the N-Cu-N interbond angles are constrained by 1) the bite angle of the BIMDPK ligand to 94 ± 2° and 2) the interligand steric interactions, which lead to the dihedral angle of the intraligand CuN2 planes of 68.2° for CuII and 74.9° for CuI-that is, a CuN4 geometry intermediate between tetrahedral and square planar. The X-band EPR spectrum for the powdered CuII compound is typical of an approximately D2 CuN4 centre possessing a dxy ground state (gx = 2.080, gy = 2.075, gz = 2.291; Az = 112.3 × 10-4 cm-1). The UV/vis spectra are dominated by charge-transfer bands, and both the CuII and CuI systems are intensely coloured. The EPR and electronic spectra indicate that these cations have a very similar structure in the solid state and in solution; the potential of the [Cu(bimdpk)2]2+/[Cu(bimdpk)2]+ couple is 0.59 V vs. SCE in MeCN and 0.80 V vs. SCE in CH2Cl2, and the electron self-exchange constant in MeCN is 1.9 × 104M-1S-1. Comparisons are made between the properties of the [Cu(bimdpk)2]2+/+ centres and related Cu centres in chmical and biological systems; the results of this study reinforce the view that a [Cu(His)4] centre should not be precluded from consideration in biological electron transport.
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  • 45
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 743-744 
    ISSN: 0947-6539
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 46
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1303-1307 
    ISSN: 0947-6539
    Keywords: bromine compounds ; cesium compounds ; crystal structure ; fluorides ; intercalation compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: CsF reacts with Br2 to form the two intercalation compounds CsF·Br2 and 2CsF·Br2. The former consists of layers of CsF squares separated by layers of Br2 molecules oriented perpendicular to the CsF layers. 2CsF·Br2 is a second-stage compound, composed of two layers of CsF followed by one layer of bromine molecules. Iodine cannot replace bromine; instead, it reacts with CsF to form Cs2I8, and probably CsIF6 between 0° and 120 °C. Chlorine does not react at all with CsF. Bromine reacts with RbF only superficially, and after a long time some RbBr3 is observed; RbF and I2 give RbI3.
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  • 47
    ISSN: 0947-6539
    Keywords: ionophores ; impedance spectroscopy ; membrane models ; monolayers ; self-assembly ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Novel ion-binding monolayers on gold surfaces are presented where the molecular design is based upon the natural ion binder ferrichrome. The new ion binders possess hydroxamate coordinating groups arranged in C2 symmetry (bishydroxamate binder, BHB) or C3 symmetry (trishydroxamate binder, THB), and a separate dialkyl sulfide moiety, which serves as an anchor to the gold substrate. The separation between the ion-binding cavity and the attachment site to the gold allows each parameter to be controlled separately, namely, cavity size, its symmetry and external envelope, as well as the functional group used for immobilization. The monolayers were characterized with respect to ellipsometric thickness, wettability (advancing and receding contact angles (CAs) for water), and surface coverage; the latter is determined by metal underpotential deposition (UPD). It is shown that the introduction of hydrophobic side chains (i-butyl) improves the CAs, thickness, and surface coverage of the monolayers. A detailed analysis of the alternating-current (AC) impedance spectra is presented for THB monolayers on gold electrodes, where the impedance data are fitted to an equivalent circuit model. It is shown that the AC response in a wide frequency range can be used to probe ion binding and release in monolayer systems on electrodes.
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  • 48
    ISSN: 0947-6539
    Keywords: crystal structure ; electronic structure ; hafnium compounds ; indium compounds ; metallic conductivity ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hf2In5 - previously reported with the tentative composition “Hf3In4” - was prepared from the elements in a tantalum tube at 970 K. The X-ray diffractional characterization by means of single-crystal refinement reveals the presence of a tetragonal structure (a = 1024.71 (9), c = 305.66 (3) pm, P4/mbm, Z = 2) of Mn2Hg5 type. Hf2In5 is Pauli-paramagnetic and a good metallic conductor. Quasi-relativistic semiempirical and scalar-relativistic ab initio band structure calculations reveal Hf2In5 to be a hafnide, composed of a two-dimensional indium network threaded by infinite hafnium chains. The amount of In-In bonding scales counterintuitively with the interatomic distances.
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  • 49
    ISSN: 0947-6539
    Keywords: asymmetric Diels-Alder reactions ; butadienes ; Diels-Alder reactions ; piperidones ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chiral 2-amino-1,3-butadienes 1 derived from commercially available (S)-2-methoxymethylpyrrolidine react with aromatic N-trimethylsilylaldimines and N-phenylaldimines in the presence of ZnCl2 to give, after the reaction workup, 4-piperidones 4 and 6, respectively, with moderate to very high enantiomeric excesses. In addition, the absolute configurations of derivatives of 4 a and 4 g were determined by circular dichroism and NMR spectroscopy on the Mosher ester, respectively.
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  • 50
    ISSN: 0947-6539
    Keywords: alkanes ; cracking ; isomerizations ; sulfur compounds ; superacids ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel family of inorganic aprotic superacids has been found. Oxochlorides and chloride of sulfur combined with aluminium halides (SOCl2·n AlX3, SO2Cl2·n AlX3, MeSO2Cl·n AlX3, CF3SO2Cl·n AlX3, S2Cl2·n AlX3; n = 2 or 3, X = Br or Cl) are found to be effective promoters for the cracking and isomerization of alkanes at room temperature.
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  • 51
    ISSN: 0947-6539
    Keywords: cyclophanes ; macrocyclisations ; molecular ribbons ; nanostructures ; repetitive syntheses ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The longest molecular ribbons known to date (3-10), composed of a series of [3.3]metacyclophane units, have been synthesised by means of a repetitive synthetic strategy. These multiple ring systems with up to nine bridged benzene rings in a row are the longest structurally perfect cyclophane sequences known to date. The synthetic strategy comprises three steps: ester reduction to a tetrakis(hydroxymethyl) compound, derivatisation to the corresponding tetrakis(bromomethyl) derivative, and double cyclisation with the new key building block 14, which was especially developed for this sequence. Single-crystal X-ray analyses (3 a-7 a) and 1H NMR spectroscopy (3-10) show that, regardless of their length, these molecules adopt zigzag folded all-syn conformations. π-Stacks of nanometre dimensions are thus formed.
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  • 52
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 752-755 
    ISSN: 0947-6539
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 53
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. cpi 
    ISSN: 0947-6539
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 54
    ISSN: 0947-6539
    Keywords: assymetric substitution ; cerium reagents ; enamino ketones ; regioselectivity ; synthetic methods ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Stereoselective construction of trisubstituted alkenes has wide applicability to the synthesis of many natual products Specifically, β-disubstituted enones are important functionalized trisubstituted alkene targets. The reaction of organocerium reagents with secondary β-enamino ketones affords β=disubsituted α,β-unsaturated ketones in fairly good yields. This process shows considerable stereoselectivity, and α,β-unsaturated ketones of (E) configuration are predominantly observed. Organolithium-derived cerium reagents display better stereoselectivity than organomagnesium-based ones. The mechanism of the reaction varies with nitrogen substitution: N-phenyl groups give 1,2-addition products, whereas substitution products are observed with N-alkyl groups. When organocerium reagents were used with β-enamino ketones bearing secondary alkyl groups at the nitrogen atom, a lack of reactivity was observed.
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  • 55
    ISSN: 0947-6539
    Keywords: clusters ; fullerenes ; nitrenes ; regio-selectivity ; valence isomerization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis, isolation, and spectroscopic characterization of the bisimino[60]fullerenes C60(NCOOR)2 (1a: R = Et, 1b. R = tBu) with a cis-1 addition pattern as well as of their regioisomeric analogues 2-7 with different addition patterns are described. Whereas compounds 2-7 are typical fulleroaziridines and obey the rule of the minimization of [5,6] double bonds, the cis-1 isomers 1a and 1b represent the first examples of fullerene derivatives with open transannular [6,6] bonds. Characteristic features within the fullerene framework of these valence isomers VI are the presence of a doubly bridged open 14-membered ring with a phenanthrene perimeter as well as of an 8-membered 1,4-diazocine heterocycle. Moreover, it is shown that, by transforming cis-1-C60(NCOOtBu)2 (1b) into cis-1-C60(NH)2 (1c), the fullerene cage can be closed in an intraring 2π→2s̰ isomerization to valence isomer V. These are the first chemical modifications of the fullerene core that allow the synthesis of both open and closed valence isomers with the same addition pattern. Density-functional as well as AM1 calculations corroborate the experimental findings that it depends on the addition pattern as well as on the nature of the addends whether or not the transannular [6,6] bonds are closed. Only in the cis-1 adducts C60(NR)2 that prefer planar imino bridges (e.g., carbamates or amides) are the open forms VI more stable than the closed isomers V.
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  • 56
    ISSN: 0947-6539
    Keywords: asymmetric eponidations ; Cstalysis ; manganese complexes ; structure elucidation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relationship between catalyst structure and enantioselectivity in the asymmetric epoxidation of unfunctionalized olefins by a series of chiral Mn(sa1en) complexes (1 - 10) was examined. The X-ray structures of 5-coordinate complexes 5, 8, of 6-coordinate 9 ([6,6′= -tBu; 4,4 = -tBu]+ClO4-), and 10 (6,6′= -tBu; 4,4′=-Br) were determined. Catalysts 1 - 9 were derived from (R,R)-1, tdiaminocyclohexane and catalyst 10 from (S,S)-1,2-diphenylethyIenediamine. Catalysts 1-9 differ in the stereoelectronic substitution of the orfho (6,6) and para (4,4) positions of the salicylidene moiety. A comparison between structures 5, 8, and 9 reveals that the ligand geometry around the metal center and the chiral diimine backbone remains remarkably constant in both five- and six-coordinate cyclohexanediamine-derived complexes; in contrast, the salicylidene regions of the complexes display a wide range of conformations. The asymmetric epoxidation of indene and 6-cyano-2,2-dimethylchromene with NaOCl catalyzed by complexes 1 - 10 was effected. Systematically increasing the steric bulk on the ortho and then the para position in the order 1 (6,6′ = -H; 4,4′ = -H),2(6,6′ = -CH3; 4,4′ = -CH3),3(6,6′=-tBu;4,4′=-H),4(6,6′=-tBu; 4,4′ =-CH3), 5 (6,6′=-tBu; 4,4′=-tBu), and 6 (6,6′=-tBu; 4,4′= -trityl), and electronically modifying the para substituents in 7 (6,6 = -tBu; 4,4 =-OMe) and 8 (6.6′ = -tBu; 4,4′=-OTIPS) resulted in enhanced enantioselectivities of the desired epoxides. The conformational variations observed in the solid state are likely to reflect accessible solution conformations and may help explain the high levels of stereoinduction obtained with these catalysts in the asymmetric epoxidation of unfunctionalized olefins.
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  • 57
    ISSN: 0947-6539
    Keywords: catalysis ; C-C coupling ; mechanistic studies ; oxidative addition ; palladium complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rates and mechanism of the reactions of a series of aryl-ligated, anionic palladium(0) complexes Ar-Pd0-(PPh3)-2 with para-substituted iodobenzenes were investigated by means of transient electrochemistry. The reaction was found to be first order in each reactant and to proceed similarly to oxidative addition of aryl halides to the halide-ligated species X-Pd0(PPh3)-2, although much faster and less sensitive to electronic factors. Owing to the short lifetime (t1/2 ≍ 1 - 5 ms) of the product of this reaction, it could not be characterized in detail. However, based on kinetic results, this transient species is thought to be an anionic pentacoordinated bisarylpalladium(II) complex, which undergoes rapid loss of halide ligand to yield, most probably, a bisarylpalladium(II) neutral species. Based on the study of this reaction and on previously reported results, we propose a mechanism for the palladium-catalyzed homocoupling of aryl halides consisting of a catalytic cycle initiated by oxidative addition of an aryl halide to a zerovalent tris-ligated palladium center. Two-electron reduction of the pentacoordinated arylpalladium(II) anionic species thus formed gives a tris-ligated anionic arylpalladium(0) center, which undergoes oxidative addition with a second aryl halide molecule to eventually lead to a bisaryl-palladium(II) neutral species. Reductive elimination of a bisaryl molecule from this center closes the catalytic cycle by regenerating the initial zerovalent palladium complex. The application of this sequence to the catalytic heterocoupling of aryl halides is discussed, and it is concluded, on the basis of Hammett correlations, that statistical yields should be observed, in agreement with the results obtained for preparative reactions in DMF.
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  • 58
    ISSN: 0947-6539
    Keywords: antithrombotics ; conformation ; molecular recognition ; oligosaccharides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An octasulfated pentasaccharide 1 having an L-iduronic acid moiety in a fixed 1C4 conformation was synthesized by the coupling of a triosyl donor 3 with a disaccharide acceptor 4 followed by deprotection and O-sulfation. The acceptor 4 was prepared from the fully acetylated 5-C-allyl-β-D-glucose building block 7 by means of a TMSOTf-promoted glycosylation, intramolecular substitution and ozonolysis of the olefinic bond as the key reactions. Compound 1 showed very low activity in an antithrombin 111-mediated anti-Xa assay; this reflects the importance of the presence of a flexible L-iduronic acid moiety in heparin-like antithrombotics.
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  • 59
    ISSN: 0947-6539
    Keywords: aminopolyols ; asymmetric aminations ; asymmetric epoxidation ; asymmetric hydroxylation ; didemnins ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel strategy for the synthesis of isostatine derivatives has been developed. Contrary to previous approaches to isostatine, a non-proteinogenic amino acid that is an essential component of the didemnins, the present synthesis does not require the intermediacy of the expensive amino acid D-allo-isoleucine, the starting material being commercially available enantiopure (S)-2-methyl-1-butanol. Steps in the sequence include catalytic asymmetric epoxidation, regioselective titanium-promoted opening of an epoxy alcohol with an ammonia equivalent, stereospecific generation of an N-Bocamino epoxide and its nucleophilic opening by a cyanide anion. Application of this method has permitted the enantioselecti