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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 102 (1969), S. 3378-3390 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Der Mechanismus der Stickstoff-Fixierung und Reduktion zu Ammoniak mittels metall-organischer Katalysatoren wird untersucht. Es wird angenommen, daß ein Titan (0)-Komplex den Stickstoff bindet und reduziert. Die Systeme (C5H5)2TiCl2/Alkalimetall eignen sich besonders für die Untersuchungen des Reaktionsmechanismus. Neben Stickstoff-Fixierung wird auch eine Wasserstoffaufnahme des Katalysators beobachtet. Die im Verlauf der Stickstoff-Fixierung auftretenden Elektronenspinresonanzspektren geben Hinweise auf die Zwischenstufen der Reaktion.
    Additional Material: 6 Ill.
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  • 2
    ISSN: 0009-2940
    Keywords: Enantiomerization ; Dynamic complexation gas chromatography ; Homofuran ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By computer simulation of experimental interconversion profiles, obtained by complexation gas chromatography, rate constants of enantiomerization have been determined for homofuran between 95 and 130°C. Since enantiomerization proceeds at similar rates in the mobile and stationary phase, the rate constants obtained by an Arrhenius plot are in excellent agreement with values determined independently by polarimetry between 60 and 90°C. We thus demonstrate that dynamic chromatography can be an easy means for the rapid determination of enantiomerization (or isomerization) barriers of ca. 70-120 kJ mol-1 requiring only minute amounts of racemic sample.
    Additional Material: 2 Ill.
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  • 3
    ISSN: 0009-2940
    Keywords: Asymmetric catalysis ; Cycloadditions ; Lewis acids ; Polymers ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A dimethylpolysiloxane chain is covalently bound to the monomeric Lewis acid catalyst (1R)-(+)-oxovanadium(1V) bis[3- heptafluorobutanoylcamphorate] [(+)-5a] at the C-10 position of the camphor moiety yielding the novel chiral polymeric (1S)-( +)-oxovanadium(1V) bis[3-heptafluorobutanoylcamphorate] -dimethylpolysiloxane [( +)-6a][1]. The Lewis acid promoted hetero Diels-Alder reaction of trans-l-methoxy-3-(trimethylsilyloxy)- 1,3-butadiene (1) and benzaldehyde (2) is studied in the presence of the enantiomerically pure monomeric (5a, 5b) and polymeric (6a, 6b) catalysts. The monomeric and polymeric catalysts of identical chirality[1] invoke opposite enantioselectivities toward the formation of 2-phenyl- 2,3-dihydro-4H-pyrone (4). This remarkable result is corroborated by numerous control experiments. Thus, it is demonstrated that the environment of the active site of the catalyst is changed when the complex is fixed to a polymeric chain. In contrast to 5 and 6, the monomeric 12 and polymeric 13 europium(III) tris[3-heptafluorobutanoylcamphorates] of identical chirality invoke the same enantioselectivity toward the formation of 4. The concept of polymer attachment is utilized to recover the catalyst from the reaction mixture by precipitation and to recycle it for subsequent catalytic runs.
    Additional Material: 4 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 101 (1968), S. 1594-1600 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Protonenresonanzspektren von Fünfringchelaten der α-Diimine, des Glyoxal-bis-hydrazons und von Ferrolen weisen auf eine cyclische Delokalisierung der π-Elektronen hin.
    Additional Material: 2 Tab.
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  • 5
    ISSN: 0899-0042
    Keywords: 2,2′-diisopropylbiphenyl ; racemization and enantiomerization ; rotational energy barrier ; computer simulation ; dynamic chiral gas chromatography ; cyclodextrin stationary phase ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By computer simulation of experimental dynamic gas chromatographic elution profiles, the rotational energy barrier ΔG= of racemic 2,2′-diisopropylbiphenyl has been determined as 114.6-115.0 kJ/mol (75-100°C). These data are in good agreement with a value that was determined previously by measuring the racemization kinetics of an enriched sample. This indicates that there is no measurable catalytic or inhibitory effect of the stationary phase. © 1994 Wiley-Liss, Inc.
    Additional Material: 2 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 9 (1997), S. 350-353 
    ISSN: 0899-0042
    Keywords: xenobiotics ; pollutants ; non-planar aromatics ; chirality ; atropisomerism ; ab initio calculations ; electron correlation ; density functional theory ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rotational barriers of overcrowded PCBs are predicted by ab initio methods including electron correlation, thus settling the controversy between theory and experiment. For 2,2′,3,3′,4,6′-hexachlorobiphenyl (PCB 132), an enantiomerization barrier of 185 kJ/mol is calculated by B3LYP/6-31G*, in excellent agreement with the experimental data. Chirality 9:350-353, 1997. © 1997 Wiley-Liss, Inc.
    Additional Material: 3 Ill.
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  • 7
    ISSN: 0899-0042
    Keywords: atropisomeric polychlorinated biphenyls (PCBs) ; Chirasil-Dex ; rotational barrier ; stopped-flow multidimensional gas chromatographic technique ; on-line enantiomerization kinetics ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rotational barriers ΔG
    Additional Material: 3 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 10 (1998), S. 140-146 
    ISSN: 0899-0042
    Keywords: enantioselective chromatography ; chiral selectands ; chiral selectors ; peak coalescence ; enantiomer separation ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Six scenarios of peak coalescence are distinguished in enantioselective chromatography. Where appropriate, they are verified by an experiment. Chirality 10:140-146, 1998. © 1998 Wiley-Liss, Inc.
    Additional Material: 6 Ill.
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  • 9
    ISSN: 0899-0042
    Keywords: configurational lability ; enantiomers ; diastereomers ; epimers ; macroscopic processes ; microscopic processes ; pharmacological time scale ; pharmaceutical time scale ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The configurational lability of enantiomers can be characterized by different terms, each defining a specific process. Racemization relates to the macroscopic and statistical process of the irreversible transformation of one of the enantiomers into the racemic mixture. Enantiomerization refers to the microscopic and molecule process of the reversible conversion of one enantiomer into the other. Methods allowing the experimental determination of rate constants of racemization (krac) and enantiomerization (kenant) are discussed, and it is shown that kenant = 1/2 krac. Neglect of this fact is a source of some confusion in the literature. When two or more elements of chirality are present in a molecule and one of them is configurationally labile, epimerization occurs, a particular case of diastereomerization. These processes of interconversion between diastereomers are kinetically more complicated than racemization and enantiomerization since the rate constants of the forward and reverse reactions are always different (kdiast/A-to-B ≠ kdiast/B-to-A), however small the difference. An important aspect of the configurational lability of stereoisomeric drugs is the time scale of the phenomenon. When interconversion occurs to a significant extent during the residence time of a drug in the body, a pharmacological time scale is implied. In contrast, the pharmaceutical time scale refers to slower rates of interconversion that affect the configurational purity of a drug during its shelf-life. © 1995 Wiley-Liss, Inc.
    Additional Material: 5 Ill.
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  • 10
    ISSN: 0899-0042
    Keywords: atropisomeric polychlorinated biphenyls (PCBs) ; Chirasil-Dex ; rotational barrier ; stopped-flow multidimensional gas chromatographic technique ; on-line enantiomerization kinetics ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rotational barriers ΔG† (T) of the four atropisomeric polychlorinated biphenyls (PCBs) 2,2′,3,5′,6-pentachlorobiphenyl (PCB 95), 2,2′3,3′,4,6′-hexachlorobiphenyl (PCB 132), 2,2′,3,3′,6,6′-hexachlorobiphenyl (PCB 136), and 2,2′,3,4′,5′,6-hexachlorobiphenyl (PCB 149) were determined via on-line enantiomerization kinetics by a new stopped-flow multidimensional gas chromatographic technique (stopped-flow MDGC) employing Chirasil-Dex as chiral stationary phase for enantiomer separation. The calculated rotational barriers ΔG† (T) of the trichloro-ortho-substituted atropisomers are 184 ± 2 kJ/mol for PCB 95, 189 ± 4 kJ/mol for PCB 132, and 184 ± 1 kJ/mol for PCB 149 at 300°C. The rotational barrier ΔG† (T) of tetrachloro-ortho-substituted PCB 136 is at least (or higher than) 210 kJ/mol at 320°C. Chirality 10:425-429, 1998. © 1998 Wiley-Liss, Inc.
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