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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 111 (1978), S. 1578-1590 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Über die konformative Präferenz in substituierten Cyclopentadienyl- und Heterocyclopentadienyl-KomplexenMO-Berechnungen ergeben erhebliche Barrieren für die internen Rotationen in Thiadiborolen-Fe(CO)3- und Diazaborolen-Cr(CO)3-Komplexen. Die Gleichgewichtsgeometrien der zwei Moleküle sollten verschieden sein. Eine MO-Fragmentanalyse erklärt diese Ergebnisse und führt darüberhinaus zu einer ganz allgemeinen Analyse der Rotationsbarrieren in Heterocyclopentadienyl- und substituierten Cyclopentadienyl-ML3- und -ML2-Komplexen. Für letztere wird ein gleitender Übergang von η5- nach η2-Koordination vorhergesagt.
    Notes: Molecular orbital calculations indicate substantial barriers to internal rotation in thiadiborolene-Fe(CO)3 and diazaborolene-Cr(CO)3 complexes. The equilibrium geometry of the two molecules should also differ. A fragment analysis explains these results and leads to a general analysis of rotational barriers in heterocyclopentadienyl and substituted cyclopentadienyl-ML3 and -ML2 complexes. In the latter an interesting “slipping” from η5 toward η2 coordination is predicted.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 111 (1978), S. 1591-1602 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cycloheptatrien- und Fulven-Cr(CO)3-KomplexeIm Tricarbonylchrom(0)-Komplex von 1,6-Methano[10]annulen und in einigen verwandten Komplexen nimmt die Cr(CO)3-Einheit verglichen mit allen anderen Hexatrien-Cr(CO)3-Systemen eine anomale Orientierung relativ zum Polyen ein. Eine theoretische Analyse dieses Problems zeigt, daß diese Vorzugskonformation eng mit der Cycloheptatrien-Norcaradien-Valenztautomerie zusammenhängt. Mögliche Wege, die Rotationsbarriere in derartigen Komplexen zu beeinflussen, werden aufgezeigt. Vorzugskonformation, Rotationsbarriere und Abknicken der exocyclischen Methylengruppe in Tricarbonyl(η6-fulven)chrom(0) werden diskutiert und die Analyse wird auf die analogen Benzyl-Cr(CO)3- und Cyclobutadiencarbinyl-Fe(CO)3-Kationen ausgedehnt. Die Konformation dieser Komplexe wird solchen gegenübergestellt, die zwei Elektronen mehr enthalten.
    Notes: 1,6-Methano[10]annulene-Cr(CO)3 and several related complexes adopt an anomalous orientation of the Cr(CO)3 unit with respect to the polyene, compared to all other hexatriene-Cr(CO)3 complexes. A theoretical analysis of this problem shows that these conformational preferences are closely related to the cycloheptatriene-norcaradiene valence tautomerism. Several strategies for influencing the barrier to internal rotation in these complexes are presented. An analysis of the conformational preference, rotational barrier, and bending of the exocyclic methylene group in fulvene-Cr(CO)3 is also discussed. This is extended to the analogous benzyl-Cr(CO)3 and cyclobutadiene-carbinyl-Fe(CO)3 cations. Finally, the orientations of these complexes are contrasted to those containing two more electrons.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The potentiometric study of the complexation of Cu2+ with 1,4,7-triazacyclononane (1), 1,4,8-triazacyclodecane (2) 1,5,9-triazacyclododecane (3) has shown that CuL, CuL2 and (CuLOH)2 are the main species present in solution. Their stabilities (Table 1) and their absorption spectra (Table 2) indicate facial coordination of the cyclic triamines in a distorted octahedral geometry.The formation and dissociation kinetics have been measured by stopped-flow techniques. The formation in acetate buffer can be described by the reaction of Cu2+ and CuAcO+ with the monoprotonated species of the ligand. The bimolecular rate constants for these complexations (Table 3) decrease when the ring size increases. In contrast the dissociation induced by acid is only little affected by the ring size. Thus for these complexes the rate of formation and not that of the dissociation determines the overall stability.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the presence of Ni2+ the template reaction between 2,6-diacetylpyridine and 4-(2-dimethylaminoethyl)- or 4-(2-hydroxyethyl)-1, 7-diamino-4-azaheptane yields the complexes of either the open-chain ligand (3 and 11) or of the macrocycle (4 and 12). Reduction of the imino group in 4 and 12 with PtO2/H2 gives 5 and 13, respectively. In the case of the dimethylamino derivative 5 a mixture of at least four isomers was obtained. These were partially separated by chromatography on Sephadex SP-25 cation exchanger. Through demetalation of the Ni2+ complexes by cyanide the new macrocycles 7 and 14 were isolated, from which the corresponding Zn2+ and Cu2+ complexes were prepared.The macrocyclic Ni2+-complexes 4, 12, 5 and 13 can exist in two forms depending on the pH of the solution. At low pH protonation of the dimethylamino or hydroxy group in the side chain occurs. The metal ion is then bound to the four nitrogen atoms of the macrocycle in a square planar ligand field. At higher pH, however, the dimethylamino or hydroxy group (the last one also in its deprotonated form) can coordinate to one of the axial positions, whereby pseudooctahedral coordination geometry is induced. This reaction can be quantitatively described by a reversible acid-base equilibrium, the pKH of which greatly depends on the nature of the functional group, the degree of unsaturation of the macrocycle and the metal ion.The acid-base reaction and the concomitant structural change are a direct consequence of the unique combination of the rigid and kinetically stable structure of the macrocycle and of the flexible and kinetically labile functional group of the side chain.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 683-688 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The complexone-like tetraazamacrocycle 1 (LH4) forms a series of metal complexes with Co2+, Ni2+, Cu2+ and Zn2+ (M2+) of the type MLH2, ML2- and M2L, which have been isolated and characterized by VIS., IR. and NMR. spectroscopy. Based on these results tentative structures for the different species are proposed.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 62 (1979), S. 2562-2568 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 10, 10, 12-Trimethyl-3,4-benzo-1,6-dithia-9,13-diazacyclopentadecen-dihydrochloride (LH22+, 2) and its Ni2+ complex were synthesized and their reactivity studied. The formation kinetics of 2 with Cu2+ were found to be a second order reaction between Cu2+ or CuACO+ and the monoprotonated form of the ligand LH+. The rate constant kCuLH = 29 M-1S-1 is 105-106 times smaller than those of monoprotonated tetraazamacrocycles either because of second bond formation or because of a strong electrostatic interaction between the positive charges of the Cu2+ and the ammonium group. The metal-metal exchange between NiL+ and Cu2+ was also investigated. The reaction is independent of [Cu2+] and has the same rate and activation parameters as the dissociation of NiL2+. In contrast to open chain ligands, no mixed complex CuNiL4+ as intermediate was observed.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Poly[sulfadiazinacrylamid] (5) mit 14C-Hauptkettenmarkierung wurde synthetisiert und sein Molekulargewicht viskosimetrisch durch Vergleich mit inaktiven Proben von Poly-[sulfadiazinacrylamid] mit membranosmometrisch ermittelten Molekulargewichten ähnlicher Größe bestimmt.In seinem systemischen Verhalten bei Mäusen zeigte die Verbindung einen polymerspezifisch protahierten Verlauf. Die Ausscheidungsraten des Polymeren waren vernachlässigbar gering, seine Toxizität erheblich. Es wurde im Untersuchungszeitraum in der Leber akkumuliert, aber eine Tumoraffinität zum PC6 Plasmazelltumor bei Mäusen war nicht feststellbar.
    Notes: Poly[sulfadiazineacrylamide] (5), labeled with 14C in the main chain, was synthesized and its molecular weight viscosimetrically determined by comparison with unlabeled samples of poly[sulfadiazineacrylamide] with similar molecular weights which were determined by membrane osmometry.The material showed a polymer-specific prolongation of its systemic behaviour in mice. Rates of excretion of the polymer were negligibly low, whereas the toxicity was considerable. It was concentrated in the liver during the course of the experiment, but no affinity toward the PC6 plasmacytoma in mice could be detected.
    Additional Material: 1 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 23 (1979), S. 201-214 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The diffusivities of simple gases through a series of polyurethane block copolymers of differing aromatic urethane content and type of soft segment were measured using a quadrapole mass spectrometer as a detecting device. Although an Arrhenius expression generally described the temperature dependence of diffusion in this system, a discontinuity was observed in the Arrhenius plots for some materials, and the discontinuity was found to be related to the onset of the glass transition in the hard domains. Increasing the hard segment content of the materials decreased the diffusivity due to the increase in the activation energy of diffusion. Increasing the soft segment length brought about a decrease in the activation energy with an increase in diffusivity. Polyster urethanes had lower activation energies for diffusion than polyether urethanes of similar hard segment composition. Finally, as the penetrant diameter was increased, a decrease in the diffusivity and an increase in the activation energy was noted.
    Additional Material: 7 Ill.
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  • 9
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 12,12-Dimethyl-1,4,7,10-tetraazacyclotridecane (I), 11,13-dimethyl-1,4,7,10-tetraazacyclotridecane (II), 11,11,13-trimethyl-1,4,7,10-tetraazacyclotridecane (III) and 1,4,7,10,12,12-hexamethyl-1,4,7,10-tetraazacyclotridecane (IV) have been synthesized and their properties are described.While the Ni2+ and Cu2+ complexes of I-III have square planar geometries, those of IV are pentacoordinate according to their absorption spectra. Similarly, while the Co2+ complex of I is octahedral and readily oxygenated, the analogous complex with IV is pentacoordinate and not sensitive to oxygen.The rate of complexation of these ligands with Cu2+ and Ni2+ decreases in the order I 〉 II 〉 III ≫ IV, indicating that the number as well as the position of the methyl groups are important. Finally for Cu2+ the formation of the thermodynamic stable end product is slown down by methyl substitution in α-position to the coordinating nitrogen atoms (ligand II and III) so that an intermediate can be observed, whereas with I Cu2+ directly forms the end product.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 61 (1978), S. 2291-2296 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The complexation kinetics of the two macrocycles 1 and 2 with Co2+, Ni2+, Cu2+ and Zn2+ have been measured by pH-stat techniques. The rates are first order in metal and ligand concentration and depend upon the pH. This results from the different reactivities of the various protonated species of the macrocyclic tetraamines. The resolved rate constants are given in Table 2.In comparison with other 14-membered cyclic aliphatic tetraazasystems 1 and 2 react more slowly with metal ions. This might be a consequence of the more rigid structure induced by the pyridine ring.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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