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  • 11
    ISSN: 0749-1581
    Keywords: 59Co NMR ; Six-coordinate complexes ; Porphyrin complexes ; Substituent effects ; Solvent effects ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A broad study of the 59Co NMR of cobalt(III) porphyrin complexes with axial amine ligands in a variety of solvents is reported. The data are presented in tabular form, as are the numerical correlations of chemical shift, δ, and line width, ω1/2, using the Kamlet-Taft equation. The dependence of δ and ω1/2 on ligand substituents is discussed. Solvent data, including mixed solvent results, indicate that general factors such as acidity, basicity, polarity and hydrogen-bonding capability are important, as are the specific nature of the functional groups on the ligands and the solvent.
    Additional Material: 10 Ill.
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  • 12
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 27 (1995), S. 1151-1164 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermal decomposition of CF2HCl has been modeled using 2,269 thermally activated reactions and 63 chemically activated processes. Thermochemical properties for the species involved are calculated using statistical mechanics and group contribution theory, and reaction rate constants are determined using transition state theory. The theoretical predictions, obtained without fitting any parameter values, afree closely with available experimental data. Also, the reactions that control the distribution of reaction products are identified, and this, in turn, permits simplification of the reaction set. Sensitivity studies show that uncertainties in the calculations do not alter the predicted trends in behavior or the main reaction pathways. © 1995 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 622 (1996), S. 845-852 
    ISSN: 0044-2313
    Keywords: Nickel orthoperiodate ; i.r., Raman spectra ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: NiH3IO6 · 6 H2O  -  Crystal Structures and Vibrational SpectraThe crystal structure of NiH3IO6 · 6 H2O has been determined by X-ray single-crystal diffraction (Pc, Z = 2, a = 516.74(9), b = 981.5(2), c = 1052.5(2) pm, β = 116.496(8)°) on the basis of 4169 unique reflections (R = 1.96%). The structure is built up of distorted Ni(H2O)62+ and H3IO62- octahedra linked by hydrogen bonding. IR and Raman spectra of both the title compound and isostructural MgH3IO6 · 6 H2O as well as of deuterated specimens are given. There are up to 14 different OH(OD) modes in the spectra of isotopically dilute samples due to the 15 different hydrogen positions of the structure. The internal modes of the meridional H3IO62- ions (pseudo C2v symmetry) are discussed with respect to that double T-shaped entity, which gives rise to only two instead of 3I—O, I—O(H), and OH stretches in the IR and Raman spectra, i.e. the same as for facial (C3v) structured ions.
    Notes: Die Kristallstruktur (Pc, Z = 2) von NiH3IO6 · 6 H2O wurde mittels Röntgen-Einkristallmessungen auf der Basis von 4169 symmetrieunabhängigen Reflexen bestimmt (R = 1,96%). IR- und Raman-Spektren von NiH3IO6 · 6 H2O und der isotypen Verbindung MgH3IO6 · 6 H2O sowie von deuterierten Präparaten werden mitgeteilt. Die Spektren isotypenverdünnter Proben zeigen bis zu 14 OH(OD)-Streckschwingungen entsprechend den 15 verschiedenen Wasserstoff-Positionen der Struktur. Die meridionalen H3IO62--Ionen (Pseudosymmetrie C2v) besitzen wegen der T-förmigen Anordnung der je 3 IO-und IOH-Gruppen nur je 2 IO-, IO(H)- und OH-Streckschwingungen in den IR- und Raman-Spektren und können daher schwingungsspektroskopisch nicht von H3IO62--Ionen mit facialer Struktur (C3v) unterschieden werden.
    Additional Material: 8 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 265-272 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reaction of OH radicals with t-amyl methyl ether (TAME) have been reinvestigated using both absolute (flash photolysis resonance fluorescence) and relative rate techniques. Relative rate experiments were conducted at 295 K in 99 kPa (740 torr) of synthetic air using ethyl t-butyl ether, cyclohexane, and di-isopropyl ether as reference compounds. Absolute rate experiments were performed over the temperature range 240-400 K at a total pressure of 4.7 kPa (35 torr) of argon. Rate constant determinations from both techniques are in good agreement and can be represented by k1=(6.32 ± 0.72) × 10-12 exp[(-40 ± 70)/T] cm3 molecule-1 s-1. Quoted errors represent 2σ from the least squares analysis and do not include any estimate of systematic errors. We show that results from the previous kinetic study of reaction (1) are in error due to the presence of a reactive impurity. Results are discussed in terms of the atmospheric chemistry of TAME. © 1993 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
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