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  • Articles  (46)
  • Inorganic Chemistry  (37)
  • Physical Chemistry  (9)
  • Gas chromatography
  • Wiley-Blackwell  (46)
  • 1975-1979  (46)
  • 1977  (46)
  • 1
    Electronic Resource
    Electronic Resource
    Gold-Komplexe von Diphosphinomethanen, III. AuII-Verbindungen durch oxidative Addition von Halogen (1977)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 110 (1977), S. 2758-2764 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Gold Complexes of Diphosphinomethanes, III. AuII Compounds by Means of Oxidative Addition of HalogenOxidative addition of halogen to the 1:2 complexes of bis(diphenylphosphino)methane and -propane with AuCl (1a, 5) leads to products which are formulated partly as AuI/AuIII compounds (2a, b), but partly also as true AuII derivatives (6a, b). The addition of iodine to the AuI complex yields an adduct of the type 4. For the characterisation of the largely insoluble materials, infrared, Mössbauer, and ESCA spectroscopy have been employed.
    Notes: Durch oxidative Addition von Halogen an 1:2-Komplexe von Bis(diphenylphosphino)methan und -propan mit AuCl (1a, 5) entstehen Produkte, die teilweise als AuI/AuIII-Verbindungen (2a, b), teilweise aber auch als echte AuII-Derivate zu formulieren sind (6a, b). Die Anlagerung von Iod an den AuI-Komplex liefert nur ein Addukt vom Typ 4. Zur Charakterisierung der fast ausnahmslos unlöslichen Substanzen wurden die Infrarot-, Mössbauer-und ESCA-Spektroskopie herangezogen.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19771100811
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  • 2
    Electronic Resource
    Electronic Resource
    Abfangreaktionen kurzlebiger Radikale, XV. Zum Mechanismus des induzierten radikalischen Zerfalls (SH2-Reaktion) von Peroxycarbonsäure-estern (1977)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 110 (1977), S. 1628-1635 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Short-Life Radicals, XV. Mechanism of the Induced Radical Degradation (SH2.Reaction) of Esters of Peroxycarboxylic AcidsBy means of carbonyl-18O labeling it is shown that the tert-butyl ester of perbenzoic acid (1) is attacked by stannyl radicals R3Sn· predominantly or, more probably, exclusively at the peroxide O-atom connected to the acyl moiety, giving stannyl esters of the benzoic acid 2 via an SH2-reaction. A subsequent exchange of the labeled O-atoms (2 ⇌ 3) may occur, but it is hindered in the sequence R = Me 〈 Et 〈 Bu 〈 Ph. Stannyl esters of carboxylic acids exchange their stannyl moieties with stannyl radicals at once even at 20°C, also with organotin hydrides (following a non-radical mechanism). Trityl radicals have only a very weak inducing effect on the decomposition of unlabeled 1: τ½ = 9.4 h instead of 17.2 h at 102°C. With dibutyl ether τ½ = 0.95 h at 100°C. A mechanism like that with R3Sn· has been established by labeling of 1.
    Notes: Durch Carbonyl-18O-Markierung im Perbenzoesäure-tert-butylester (1) wurde festgestellt, daß Stannyl-Radikale R3Sn· bei der zu Benzoesäure-stannylestern 2 führenden SH2-Reaktion zumindest überwiegend, wahrscheinlich ausschließlich am acylseitigen O-Atom der Peroxidbrücke angreifen. Ein nachträglicher Austausch der Markierung (2 ⇌ 3) kann auftreten, ist jedoch erschwert in der Reihe R = Me 〈 Et 〈 Bu 〈 Ph. Carbonsäure-stannylester tauschen ihre Stannylreste sofort schon bei 20°C mit Stannyl-Radikalen aus, ebenso mit Organozinnhydriden (hier nichtradikalisch). Trityl-Radikale induzieren den Zerfall von nichtmarkierter Verbindung 1 nur sehr schwach: τ½ = 9.4 h statt 17.2 h bei 102°C. Dibutylether erzielt τ½ = 0.95 h bei 100°C. Markierung in 1 erwies einen gleichen Mechanismus wie bei R3Sn·.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19771100506
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  • 3
    Electronic Resource
    Electronic Resource
    Orientierungseffekte auf Charge-Transfer-Wechselwirkungen, VII. Weitere Donor-Akzeptor-[2.2]Paracyclophane des Chinhydron-Typs (1977)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 110 (1977), S. 3351-3357 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Orientation Effects on Charge-Transfer Interactions. VII. Further Donor-Acceptor [2.2]Paracyclophanes of the Quinhydrone TypeAs further donor-acceptor [2.2]paracyclophanes with different donor-acceptor orientation, the diastereomeric pairs ¾ and ⅚ were synthesized: 3 was formed when tetrahydroxy[2.2]paracyclophane (obtained by hydrogenation of 7) was methylated uncompletely and then oxidized; 3 was also prepared from 8 by hydrolysis of the Birch reduction product 9;4 was obtained analogously starting from 10.5 and 6 were synthesized by silylation of 1 and 2. - In agreement with the results reported for the [2.2]paracyclophane quinhydrones ½, the pseudo-ortho compounds 3 and 5 show, in comparison with the pseudogeminal isomers 4 and 6, resp., for the long-wavelength charge-transfer absorption (400-600 nm) an intensity reduction by about a factor of ten and an additional charge-transfer absorption around 350 nm.
    Notes: Als weitere Donor-Akzeptor-[2.2]Paracyclophane mit unterschiedlicher Donor-Akzeptor-Orientierung wurden die Diastereomeren-Paare ¾ und ⅚ dargestellt: 3 entstand, als das durch Hydrierung von 7 erhaltene Tetrahydroxy[2.2]paracyclophan unvollständig methyliert und anschließend oxidiert wurde, sowie aus 8 bei der Hydrolyse des Birch-Reduktionsproduktes 9;4 erhielt man entsprechend ausgehend von 10.5 und 6 wurden durch Silylierung von 1 und 2 dargestellt.  -  Wie bei den [2.2]Paracyclophan-Chinhydronen ½ zeigen die pseudo-ortho-Verbindungen 3 und 5 im Vergleich zu den pseudogeminalen Isomeren 4 bzw. 6 eine etwa zehnfach geringere Extinktion der langwelligen Charge-Transfer-Bande im Bereich 400-600 nm sowie eine zusätzliche Charge-Transfer-Absorption um 350 nm.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19771101014
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  • 4
    Electronic Resource
    Electronic Resource
    Some Reactions of OH(v = 1) (1977)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 9 (1977), S. 111-122 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of OH(v = 1) with HBr, O, and CO have been studied at 295°K using a fast discharge flow apparatus: The reaction O + HBr → OH(v = 1) + Br was used as a source of OH(v = 1), and subsequent chemical reactions of the excited radical were followed using EPR spectroscopy. Rate constants for reactions (2b), (3b), and (6b) were measured as (4.5 ± 1.3) × 10-11, (10.5 ± 5.3) × 10-11, and 〈5 × 10-12 cm3/molec·sec, respectively. The rate constant for physical deactivation of OH(v = 1) by CO was determined as 〈4 × 10-13 cm3/molec·sec.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550090110
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  • 5
    Electronic Resource
    Electronic Resource
    Kinetics of the reaction of atomic hydrogen with methyl hydroperoxide (1977)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 9 (1977), S. 267-282 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction H + CH3OOH was investigated under conditions of excess atomic hydrogen concentration using a flow reactor attached to a photoionization mass spectrometer. The rate coefficient of the reaction was determined as \documentclass{article}\pagestyle{empty}\begin{document}$$ k = (2.8 \pm 0.9) \times 10^{- 13} {\rm exp\,}[- (1860 \pm 190){\rm cal}/RT \cdot {\rm mol\,}]\,{\rm cm}^3 /{\rm molec} \cdot {\rm sec} $$\end{document} The three important reaction channels were found to be with the individual contributions determined as indicated. The product methoxy and methylperoxy radicals react mainly with atomic hydrogen under the employed experimental conditions according to where the estimates for the percentage contributions of the various channels were derived from the measured product yields.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550090210
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  • 6
    Electronic Resource
    Electronic Resource
    Consecutive, irreversible first-order reactions. Ambiguities and practical aspects of kinetic analyses (1977)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 9 (1977), S. 535-548 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The general problem of eliciting reliable rate constants from experimental data is considered in detail for consecutive reactions. Practical aspects are emphasized.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550090404
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  • 7
    Electronic Resource
    Electronic Resource
    Reaction between nitrous acid and hydrogen peroxide in perchloric acid medium (1977)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 9 (1977), S. 629-640 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic investigation on the reaction has been carried out in HClO4 medium under different conditions. A spectrophotometric method of estimation of nitrous acid at various time intervals has been employed. The results are interpreted on the basis ofthe following mechanism: The absolute rate constant value of 39.7 M-1 plusmn; s-1 for k4 and the equilibrium constant Keq = 116M-1 for reaction (2) have been evaluated. The activation energy of the overall reaction has also been determined as Ea = 13.2 kcal/mol.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550090411
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  • 8
    Electronic Resource
    Electronic Resource
    On the mechanism of interaction between copper (I) and O2 (1977)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 9 (1977), S. 983-1005 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of the interaction of Cu+-α,α-dipyridyl complex (Cu+L2) with O2 in both neutral and acid media was studied by the stopped-flow method. The dependence of the mechanism on the acidity of the medium was established. In an acid medium H+ participated in a direct O2 reduction to HO2 by interaction with an oxygen adduct L2Cu+O2 formed without displacement of ligand molecules. In a neutral medium the reaction rate was limited by inner sphere charge transfer from Cu+ to O2 to form an oxygen “charge transfer” complex L2CuO+2. The latter interacted either with the second ion Cu+L2 or with the free ligand, or else it dissociated, reversibly or irreversibly, to form a radical anion O-2. The bimolecular rate constants of the oxygen “adduct” and “charge transfer” complex formation appeared to be kbi = (1.0 ± 0.1) × 105 and (1.5 ± 0.2) × 104M-1ċsec-1, respectively. The effective termolecular rate constants of O2 reduction to HO2 in an acid medium (with contribution from H+) and to O-2 in a neutral medium (with contribution from α,α-dipyridyl) were kter = 2.7 × 108 and 107M-2ċsec-1. The rate constants of the elementary steps were estimated. The auto-oxidation mechanism of the aquoion and complexes of Cu+ is discussed in terms of the results obtained.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550090612
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  • 9
    Electronic Resource
    Electronic Resource
    Luminescence de l'Europium Divalent dans les Fluosilicates MSiF6 (M = Sr, Ba) (1977)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 431 (1977), S. 31-38 
    Details
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Luminescence of Eu2+ Ions in Fluosilicates MSiF6 (M = Sr, Ba)A pure f → f emission is detected in Eu2+ doped SrSiF6 and BaSiF6. Because of the strong ionic bonding of europium a large gap occurs between the bottom of the 5d band and the 6P7/2 emission level (3000 cm-1 at 300 K). The emission is very intense under low pressure mercury excitation and decreases slowly with temperature.
    Notes: Les fluosilicates SrSiF6 et EuSiF6 ont été mis en évidence. Ils sont isotypes de la phase homologue du baryum. La luminescence de l'europium dans ces composés a été étudiée. L'émission se présente sous la forme de raies très intenses dues à des transitions internes à la configuration 4f7. L'absence de l'émission d → f usuelle s'explique par l'écart d'énergie important (3000 cm-1 à 300 K) entre le niveau 6P7/2 (4f7) et le bord inférieur de la bande 5d; celui-ci résulte du fait que le champ des ligandes et l'effet néphélauxétique sont exceptionnellement faibles vu le caractère fortement ionique de la liaison europium-fluor.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19774310103
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  • 10
    Electronic Resource
    Electronic Resource
    Studies on the Hydrolysis of Nitrosotrichlororhenium (1977)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 431 (1977), S. 268-272 
    Details
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Untersuchungen zur Hydrolyse des NitrosotrichlororheniumsHydratisiertes Nitrosotrichlororhenium, Re(NO)Cl3 · xH2O, kann nicht zur wasserfreien Verbindung getrocknet werden. Dabei wird HCl abgegeben und [Re(H2O)(NO)(OH)Cl2] bzw. [Re(H2O)0,5(NO)(OH)2Cl] in Abhängigkeit von den Bedingungen gebildet. Potentiometrische Untersuchungen zeigten, daß in wäßrig-äthanolischen Lösungen der Trichlorokomplex sehr schnell zwei Äquivalente Wasserstoffionen frei setzt, während die Abspaltung der Chloridionen zeitabhängig ist. Zwei Äquivalente an Chloridionen sind jedoch im Gleichgewichtsystem vorhanden. Das dritte Chloratom ist fest an das Rheniumatom gebunden. Eine Struktur mit Chlor-Brückenbindung wird vorgeschlagen.
    Notes: Hydrated nitrosotrichlororhenium, Re(NO)Cl3 · sH2O cannot be desiccated to the anhydrous product. Hydrogen chloride is expelled and [Re(H2O)(NO)(OH)Cl2] and [Re(H2O)0.5(NO) (OH)2Cl] are produced depending on the conditions of the reactions. Potentiometric studies have indicated that in aqueous ethanolic solutions, the trichloro complex rapidly liberates two equivalents of hydrogen ions while the release of chloride ions are time dependent. Two equivalents of chloride ions are, however, present in a equilibrium system. The third chlorine atom is rigidly bound to the rhenium atom. A chloride bridged structure has been proposed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19774310130
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