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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1547-1553 
    ISSN: 1434-1948
    Keywords: Imidazaboles ; Carbene-borane adducts ; Azole-borane adducts ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation and characterization of five new imidazabole derivatives is reported: 1,5-dibenzyl-4,4,8,8-tetrahydroimidazabole (2), 4,4,8,8-tetrafluoro-1,5-dimethylimidazabole (3), 4,4-difluoro-8,8-dihydro-1,5-dimethylimidazabole (4), 4,4,8,8-tetrachloro-1,5-dimethylimidazabole (5), and 4,4,8,8-tetraethyl-1,5-dimethylimidazabole (6). The structures of compounds 2-6 as dimeric carbene-borane adducts rather than dimeric N-borane adducts are discussed on the basis of NMR (2-6) and X-ray diffraction data (2, 3, 5 and 6).
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  • 2
    ISSN: 1434-1948
    Keywords: Alkaline earth metals ; Group-13 metals ; Coordination chemistry ; Bis(3,5-di-tert-butyl-1-hydroxy-2-phenyl)amine ligand ; Nonacoordinated strontium compound ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of 3,5-di-tert-butylcatechol and aqueous ammonia with boron, aluminum, gallium, or strontium chloride, or with calcium or barium acetate produce, under oxidizing conditions, neutral complexes of stoichiometric formulae ML (M = BCl), ML2, [M = Al (2), Ga (3), Ca (4), and Ba (5)], and ML3H [M = Sr (6)] [L = different oxidation states of bis(3,5-di-tert-butyl-1-hydroxy-2-phenyl)amine]. The structures of 1 and 4-6 were established by 1H- and 13C-NMR spectroscopy and of 2, 3, and 6 by X-ray diffraction. The coordination compound ClBL (1) was obtained by transmetallation of ZnL2 with BCl3. It is a tetracyclic compound with tetracoordinated boron and nitrogen atoms, the ligand being in the reduced form, bis(hydroxyphenyl)amine. The paramagnetic complexes 2 and 3 crystallized in the triclinic system and are hexacoordinated with two orthogonal planar ligands bonded to the metal atoms. The ligands appear in two different oxidation states: one as the monoanion and another as a radical dianion. Based on their X-ray diffraction molecular structures, it is deduced that both ligands have similar structures, confirming electronic delocalization and fast interconversion of their oxidation states. Ca and Ba complexes are diamagnetic and hexacoordinated, both ligands being monoanions The strontium complex crystallized in the monoclinic system, the metal atom is nonacoordinated, having two ligands as monoanions, and a third one is a neutral protonated diquinone. Its structure is a distorted helix with three paddles in a C3 geometry and its unexpected diamagnetic behaviour is due to the presence of a reduced protonated ligand.
    Additional Material: 4 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 3 (1997), S. 1017-1024 
    ISSN: 0947-6539
    Keywords: autocatalysis ; coiled coil ; kinetics ; peptides ; self-replication ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A 32-residue α-helical peptide with a sequence similiar to that of the GCN4 leucine zipper region is shown to catalyze its own formation by accelerating the amide bond formation of a 17-residue peptide, preactivated as a thiobenzyl ester, and a 15-residue peptide with a N-terminal cysteine. The self-replication process displays parabolic growth characteristics as revealed by a detailed kinetic analysis. Control reactions with single-mutant peptides strongly support a mechanism in which a ternary and/or quaternary complex of the product with both peptide fragments act(s) as the catalytically active intermediate(s). Furthermore, these experiments reveal a remarkable sequence selectivity, as evidenced by the loss of autocatalytic activity as a result of a single replacement of leucine or valine residues with an alanine at the recognition interface.
    Additional Material: 11 Ill.
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  • 4
    ISSN: 1434-1948
    Keywords: Trinuclear triangulo palladium complex ; 2-Hydroxyacetophenone N4-ethylthiosemicarbazone ; Dimethylformamide aggregation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The X-ray crystal structure of a palladium(II) complex of 2-hydroxyacetophenone N4-ethylthiosemicarbazone (H2Ap4E) shows it to be a triangular,trinuclear complex with bridging thiosemicarbazonato sulfur atoms. This species can be formed from a monomer on dissolution in DMF or directly from Li2PdCl4 and the thiosemicarbazone in methanol-ammonia solution.
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  • 5
    ISSN: 1434-1948
    Keywords: Palladium ; Platinum ; Aryl rotation ; Through-space coupling interactions ; Turnstile mechanism ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The square-planar complexes [MR2L2] (M = Pd, Pt; R = 3,5-C6Cl2F3) [L2 = OPPyPh2 (Py = 2-pyridyl); SPPyPh2; OPPy2Ph; DMBI (3,3′-dimethyl-2,2′-biindazole); OPPyPh(NHTol-p); p-TolNPPy2Ph] have been prepared by treating cis-[MR2(THF)2] (THF = tetrahydrofuran) with the appropriate chelate ligands. The 19F-NMR spectra of these complexes show the presence of intramolecular through-space F-F couplings between ortho-fluorine atoms of nonequivalent R groups, which provide information for the assignment of the different ortho-fluorine signals and can be used to study the dynamic behavior of the mentioned complexes such as: a) Rotation of the R group in either Pd or Pt complexes, at the same or at different rates for each R groups depending on the neutral ligand; and b) exchange of the coordination sites of the chelating ligand, either by Berry or by turnstile mechanisms. The activation parameters for some of the processes are given.
    Additional Material: 9 Ill.
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  • 6
    ISSN: 1434-1948
    Keywords: Ruthenium ; Thiolate ligands ; Dithiolate ligands ; Substitution reactions ; Electrophilic additions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The known dithiolate-bridged ruthenium(I) complex [Ru2(μ-bdt)(CO)6] (1) (bdt = benzene-1,2-dithiolate) has been prepared in fair yield (55%) by the sequential treatment of RuCl3·nH2O with carbon monoxide, benzene-1,2-dithiol and zinc in a one-pot reaction. Complex 1 reacts readily with monodentate phosphanes to give, stepwise, the penta- and tetracarbonyl derivatives [Ru2(μ-bdt)(CO)6-n(PR3)n] (n = 1, 2; R = Ph, Cy, iPr). However, the reaction of 1 with one equivalent of bis(diphenylphosphanyl)methane (dppm) affords a mixture of complex 1 and the disubstituted derivative [Ru2(μ-bdt)(CO)4(η1-dppm)2], in which the dppm ligands are monodentate. This mixture is subsequently transformed into a polymeric material of formula [{Ru2(μ-bdt)(CO)4}(μ-dppm)]n, which consists of binuclear {Ru2(μ-bdt)(CO)4} units linked to each other by bridging dppm ligands. The use of two equivalents of dppm leads to [Ru2(μ-bdt)(CO)4(η1-dppm)2] in quantitative yield. The X-ray diffraction structure of [Ru2(μ-bdt)(CO)4(PiPr3)2] (3c) confirms that the phosphane ligands are located in axial positions, cis to both sulfur atoms, and that the Ru-Ru distance is short [2.6753(7) Å]. A comparative study of the reactivity of complexes 1 and 3c with the electrophiles H+, [Au(PPh3)]+, and HgCl2 has allowed the isolation of the derivatives [Ru2(μ-H)(μ-bdt)(CO)6-n(PiPr3)n][BF4] (n = 0, 2), [Ru2Au(μ-bdt)(CO)6-n(PiPr3)n(PPh3)][BF4] (n = 0, 2) and [Ru2HgCl2(μ-bdt)(CO)6-n(PiPr3)n] (n = 0, 2), respectively.
    Additional Material: 1 Ill.
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  • 7
    ISSN: 1434-193X
    Keywords: Natural products ; Steroids ; Chenodeoxycholic acid ; Brassinosteroid analogues ; Biological activity ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and spectroscopic characterization of two new bioactive analogues of brassinosteroids with a 24-hydroxylated cholanic side chain, an A/B ring cis-junction and oxygenated functions in C-7 is described.
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  • 8
    ISSN: 1434-193X
    Keywords: Dicarboxylic amino acids ; Amidation reactions ; Candida antarctica lipase ; Enzyme catalysis ; Regioselectivity ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Diethyl esters of both (R)- and (S)-N-blocked α-aminoadipic and α-aminopimelic acids yield exclusively the ω-monoamide when they are subjected to amidation catalysed by the lipase B of Candida antarctica in anhydrous diisopropyl ether. These results are in contrast to the α-monoamide yielded by the equivalent L-glutamic derivatives under the same experimental conditions. These results show that the length of the side chain plays a crucial role in the regioselectivity of the reaction.
    Additional Material: 3 Tab.
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  • 9
    ISSN: 1434-193X
    Keywords: Proteins ; Cross coupling ; Drug research ; Photochemistry ; Toxicology ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -To gain insight into the chemical nature of drug-induced photoallergy, model studies have been carried out on the photochemical modification of proteins by tiaprofenic acid. Irradiation of decarboxylated tiaprofenic acid (DTPA) in the presence of p-cresol leads to C-C- and C-O-connected p-cresol “dimers”, together with DTPA hydrodimers. The p-cresol-DTPA cross-coupling product was not detected in this reaction. However, a product of this type is formed using a more hindered phenol, such as 2,6-di-tert-butylphenol. Similar results are obtained when tiaprofenic acid (TPA) or its methyl ester are used as photosensitizers. The observed formation of “dimers” can be related to protein photo-crosslinking, through the coupling of two tyrosine units. On the other hand, phenol-(D)TPA cross-coupling may be relevant to the understanding of drug-protein photobinding.
    Additional Material: 5 Ill.
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  • 10
    ISSN: 1434-1948
    Keywords: Ruthenium ; Osmium ; Phosphane-thiolate ligands ; C-P bond activation ; C-S bond activation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-(Diphenylphosphanyl)thiophenol (HSC6H4PPh2) reacts with the carbonyl clusters [Ru3(CO)12] and [Os3(CO)10(MeCN)2] to give mixtures of products, the composition of which depends upon the reaction conditions and the ratio of the reactants. The derivatives [M3(μ-H)(μ-η2-SC6H4PPh2)(CO)9] (1a: M = Ru; 1b: M = Os), [Ru3(μ3-S)(μ-η2-Ph)(μ-PPh2)(PPh3)(CO)6] (2), and [Ru2(μ-η2-SC6H4PPh2)2(CO)4] (3) have been isolated. The SC6H4PPh2 ligand of compounds 1a and 1b has the sulfur atom spanning the same M-M edge as the hydride ligand and the phosphorus atom attached to one of the bridged metal atoms. Compound 2, which contains sulfide, phenyl, diphenylphosphanyl and triphenylphosphane ligands that arise from HSC6H4PPh2, has the Ru3 triangle capped by the sulfide and two Ru-Ru edges spanned by bridging phenyl and diphenylphosphanyl ligands. In complex 3, the two SC6H4PPh2 ligands have the same coordination behavior as in 1a or 1b; this binuclear complex is more conveniently prepared by treating [Ru2(μ-η2-MeCO2)2(CO)4(MeCN)2] with HSC6H4PPh2.
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