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  • Inorganic Chemistry  (809)
  • Physics Chemistry  (51)
  • 1990-1994
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  • 1990-1994
  • 1970-1974  (860)
  • 1955-1959
  • 1930-1934
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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 3
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reinvestigation of the gas phase thermal reaction of 1,1,2,2-tetramethylcyclopropane (699-759°K) gave for the unimolecular disappearance of reactant, k(TMC) = 1015.27-63.93/θ sec-1, in good agreement with the original results of Frey and Marshall. However, evidence for a high activation energy (E = 79 ± 5 kcal/mole), competitive unimolecular decomposition to 2,3-dimethyl-1 and -2-butenes was also obtained. It is proposed that the serious discrepancy noted [1] between the experimentally observed Arrhenius parameters for the overall reaction kinetics, and those predicted by transition state calculations assuming a biradical mechanism for the isomerization reactions (previously believed to be the only primary reaction mode) can be explained in terms of the increasing importance of the decomposition reactions at higher reaction temperatures.
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  • 4
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dilute mixtures of 4-methyl-l-pentyne have been pyrolyzed in a single-pulse shock tube. The decomposition process involves bond breaking: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm HC} \equiv {\rm C} - {\rm CH}_2 ({\rm i - C}_{\rm 3} {\rm H}_{\rm 7} )\stackrel{k_B}{\longrightarrow}{\rm HC} \equiv {\rm C} - {\rm CH}_2 \cdot ({\rm propynyl}) + {\rm i - C}_{\rm 3} {\rm H}_{\rm 7} \cdot $$\end{document} as well as a molecular reaction: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm HC}\equiv {\rm C} - {\rm CH}_{\rm 2} ({\rm \rm i - C}_{\rm 3} {\rm H}_{\rm 7} )\stackrel{k_M}{\rightarrow}{\rm C}_{\rm 3} {\rm H}_4 ({\rm allene}) + {\rm C}_3 {\rm H}_6 . $$\end{document} The rate parameters are: \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\bf B} = 10^{15.56} \exp {\rm (} - 34,940/T){\rm (sec}^{ - {\rm 1}}) $$ $$\begin{array}{*{20}c} k_{\rm M} = 10^{13.1} \exp {\rm (} - {\rm 29,670/}T){\rm (sec}^{ - {\rm 1}})&{\rm 1100}^ \circ {\rm K, 1}{\rm .5} - 5{\rm atm}\end{array}$$\end{document} The heat of formation of propynyl radical is thus ΔHf300 = 338 kJ mol-1 (80.7 kcal mol-1)· This leads to a propynyl resonance energy of 40 kJ mol-1 (9.6 kcal mol-1).
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  • 5
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas-phase reaction CH3COCH3 + I2 ⇄ CH3COCH2I + HI have been measured spectrophotometrically in a static system over the temperature range 340-430°. The pressure of CH3COCH3 was varied from 15 to 330 torr and of I2 from 4 to 48 torr, and the initial rate of the reaction was found to be consistent with \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CH}_3 {\rm COCH}_3 + {\rm I}^{\rm .} \stackrel{1}{\rightarrow}{\rm CH}_{\rm 3} {\rm COCH} + {\rm HI} $\end{document} as the rate-determining step. An Arrhenius plot of the variation of k1 with temperature showed considerable scatter of the points, depending on the conditioning of the reaction vessel. After allowance for surface catalysis, the best line drawn by inspection yielded the Arrhenius equation, log [k1/(M-1 sec-1)] = (11.2 ± 0.8) - (27.7 θ 2.3)/θ, where θ = 2.303 RT in kcal/mole. This activation energy yields an acetone C—H bond strength of 98 kcal/mole and δHf0 (CH3COĊH2) radical = -5.7 ± 2.6 kcal/mole. As the acetone bond strength is the same as the primary C—H bond strength in isopropyl alcohol, there is no resonance stabilization of the acetonyl radical due to delocalization of the radical site. By contrast, the isoelectronic allyl resonance energy is 10 kcal/mole, and reasons for the difference are discussed in terms of the π-bond energies of acetone and propene.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the ethane pyrolysis have been studied at temperatures from 550 to 596°C and with 0 to 62% of added nitric oxide. The rates of production of various products were studied by gas chromatography; ethylene, hydrogen, methane, nitrogen, water, nitrous oxide and acetonitrile were found as primary products, with hydrogen cyanide, carbon monoxide, acetaldehyde, n-butane, 1-butene, cis- and trans-2-butene and 1,3-butadiene as secondary products. For all the primary products the orders with respect to C2H6and NO were determined, as were the activation energies at two different percentages of NO (15.7 and 45.5%).Nitric oxide was found to be rapidly consumed with a finite initial rate, and the rate of production of H2O was close to that of C2H4 at higher nitric oxide pressures.A mechanism is proposed which gives good agreement with all of the observed results. Its main features are: (1) Initiation takes place mainly by the unimolecular dissociation of ethane; there is no evidence for or against the process NO + C2H6 → HNO + C2H5; (2) NO scavenges ethyl radicals to form acetaldoxime which decomposes, and in this way the breakdown of C2H5 is hastened; (3) termination takes place mainly by the unimolecular decomposition of acetaldoxime to give inactive products. Some of the relevant rate parameters are evaluated. Reactions are proposed to account for the formation of the secondary products observed.
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  • 7
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 8
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 11
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 12
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 13
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 14
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas-phase dehydrogenation of cyclopentane to cyclopentene is found to be consistent with a slow attack by an I atom (step 4, text) on cyclopentane in the range 282-382°C. The measured rate constants fit the Arrhenius equation, log k4 = 11.95 ± 0.08 - (24.9 ± 0.23)/θ 1 mole-1 sec-1, where θ = 2.303RT in kcal/mole. This leads to a value of ΔHf,2980 = 24.3 ± 1 kcal/mole and a bond dissociation energy DH = 94.9 ± 1 kcal/mole. The latter value is identical with DH0(i-Pr-H) = 95 ± 1 kcal/mole and signifies that cyclopentane and the cyclopentyl radical have the same strain energy. Arrhenius parameters are deduced for all six steps in the reaction mechanism. Surface reactions are shown to be unimportant.Cyclopentyl iodide is an unstable intermediate in the reaction and the rate constant for its bimolecular formation from HI + cyclopentene is found to be log k6 = 8.40 ± 0.29 - (26.9 ± 0.8)/θ 1 mole-1 sec-1. Together with the equilibrium constant, this yields for the unimolecular elimination of HI from cyclopentyl iodide, the rate constant, log k5 = 13.3 ± 0.3 - (42.8 ± 1.2)/θ sec-1.
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  • 15
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absolute rate constants have been measured for several gas-phase chlorine atom-molecule reactions at 25°C by resonance fluorescence. These reactions and their corresponding rate constants in units of cm3 mole-1 sec-1 are: The effects of varying the substrate pressure, total pressure, light intensity and chlorine-atom source on the value of the bimolecular rate constants have been investigated for all these reactions. Conditions under which no competing side reaction occurs were established and the reported rate constants were measured under these conditions. For reactions (2), (5), (6), (7), and 8, there is a discrepancy of a factor of two between the rate constants measured in this work and values in the literature; it is suggested that this is due to an error in the previously measured value of kCH4/kH2 upon which the relative measurements in the literature ultimately depend.
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  • 16
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: At 540°C, H2S (0.1 to 5 mm Hg) diminishes the initial rate of pyrolysis of C2H6 (50 mm Hg) into C2H4 + H2 and, even more strongly, the rate of appearance of the traces of nC4H10; on the contrary, the initial rate of formation of the traces of CH4 is practically not modified.A mechanism is proposed in order to interpret these experimental facts.
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  • 17
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase dehydrogenation of cyclopentene to cyclopentadiene catalyzed by iodine in the range 178-283°C has been found to obey a rate law consistent with the slow rate-determining step, \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm I} + {\rm c} - {\rm C}_5 {\rm H}_8 \stackrel{4}{\rightarrow}{\rm HI} + {\rm c} - {\rm C}_5 {\rm H}_7 $\end{document}, log [k4/(1 mole-1 sec-1)] = 10.25 ± 0.08 - (12.26 ± 0.18)/θ, where θ = 2.303RT in kcal/mole. Surface effects are not important. This value of E4 leads to a value of DHf2980 = 82.3 ± 1 kcal/mole and ΔHf298 = 38.4 ± 1 kcal/mole. From difference in bond strengths in the alkane and the alkene, the allylic resonance stabilization in the cyclopentenyl radical is 12.6 ± 1.0 kcal/mole, in excellent agreement with the value for the butenyl radical.Arrhenius parameters for the other steps in the mechanism are evaluated. The low value of A4 (compared with A4 for cyclopentane) suggests a “tighter” transition state for H-atom abstraction from alkenes than from alkanes.
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  • 18
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 19
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of 1,2-dichloropropane at atmospheric pressure has been studied in the temperature range 227-590°C, in a flow system. Above 450°C, the reaction is homogenous and unimolecular with a rate constant: \documentclass{article}\pagestyle{empty}\begin{document}$$k = 10^{12.95 \pm 0.15} \exp (- 53,070 \pm 500/RT)\sec ^{ - 1}$$\end{document}Below 450°C, a low activation energy, probably heterogenous process competes with the gas phase reactionThe primary reaction products are HCl and the monochloropropene isomers; the relative amounts of each isomer depend on the temperature in the low but not in the high temperature region. The direction of the HCl elimination is discussed in terms of substituent effects at the α- and β-carbon positions and compared with literature data on similar reactionsSecondary products are formed principally by further pyrolysis of allyl chloride. The first-order rate constant of this reaction is given by: \documentclass{article}\pagestyle{empty}\begin{document}$$ k = 10^{8.54 \pm 0.2} \exp (- 37,275 \pm 700/RT)\sec ^{ - 1} $$\end{document}.
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  • 20
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A record of the time dependence of the difference between two signals, one proportional to the concentration of a reactant or product in one reaction mixture and the other proportional to the concentration of the same or a corresponding substance in another mixture in which the reaction is initiated at the same time as the first, makes it possible to obtain not only the ratio, but also the individual values, of the rate constants for the two reactions. The effects of the experimental variables on a number of measurable parameters are examined, the errors associated with a number of different ways of evaluating the rate constants and their ratio are discussed, and it is shown how conditions can be selected that should provide values whose precisions compare favorably with those attainable by other techniques.
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  • 21
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and absolute rate constants for the free-radical chain reaction of tri-n-butyltin hydride with di-t-butyl disulfide have been measured in cyclohexane at 30°. The rate controlling step for chain propagation involves the cleavage of the disulfide bond by an attacking tributyltin radical. The rate constant for this bimolecular homolytic substitution at sulfur is ∼8 × 104 Mole-1 sec-1. Chain termination involves the self-reaction of two tributyltin radicals.The rate constants for attack of tributyltin radicals on some other disulfides and on elemental sulfur have also been measured. The results are compared with literature data for homolytic substitutions on these compounds by a variety of radicals which have their unpaired electron centered on carbon.
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  • 22
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    New York, NY : Wiley-Blackwell
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 23
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    New York, NY : Wiley-Blackwell
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nitrogen quantum yields are reported for the photolysis of C2F5N=NC2F5 at 3660 Å over the pressure range 2-10 cm from 25° to 150°c. The Stern-Volmer plots obtained are discussed and compared with those obtained with azoethane and azoisopropane.
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  • 24
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    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method for constructing potential energy surfaces previously proposed by the author has been extended to hydrogen transfer reactions between halide, oxygen, and carbon atoms. A qualitative relation was found between the repulsive energy and the number of anti-bonding electrons. In general, the calculated kinetic isotope effect is in satisfactory agreement with observed values and the contributions by H-atom tunneling to the rate of reaction is smaller than that obtained from other surfaces.
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  • 25
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    New York, NY : Wiley-Blackwell
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: O(1D), produced from the photolysis of N2O at 2139 Å, reacts with N2O in accord with: \documentclass{article}\pagestyle{empty}\begin{document} $$ \begin{array}{*{20}c} {(2)} & {{\rm O}(^1 D) + N_2 {\rm O} \to {\rm N}_2 + {\rm O}_2 } \\ \end{array} $$ \end{document}\documentclass{article}\pagestyle{empty}\begin{document} $$ \begin{array}{*{20}c} {(3)} & { \to 2{\rm NO}} \\ \end{array} $$ \end{document}We have used the method of chemical difference to obtain an accurate measure of k2/k3 = 0.59 ± 0.01. Furthermore, the quantum yield of production of O(3P), either on direct photolysis or on deactivation of O(1D) by N2O, is less than 0.02 and probably zero.
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  • 26
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the decomposition of benzotrifluoride was studied from 720°c to 859°c in a flow system with and without carrier gas. Consideration of the product distribution made possible the study of the decomposition into CF3 and C6H5 radicals, which appeared to be truly homogeneous in character. The first-order rate constant of the C—C bond fission, log k (sec-1) = (17.9 ± 0.5) (99.7 ± 2.5)/θ, did not change with change of initial concentration, pressure of the carrier gas, or contact time. The Arrhenius parameters have been related to the appropriate thermodynamic data. Assumption of 0 kcal/mole for the activation energy of the reverse combination reaction yielded DH298°(C6H5—CF3) = 103.6 ± 2.5 kcal/mole and ΔHf298°(C6H5) = 77.1 ± 3.0 kcal/mole.Applicability of the simple first-order formula to calculation of the rate constant has been also dealt with.
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  • 27
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    New York, NY : Wiley-Blackwell
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of trifluoromethyl radicals with ammonia in the gas phase has been studied in the temperature range 30-352°. Product formation is not explicable simply in terms of the reactions: \documentclass{article}\pagestyle{empty}\begin{document}$\begin{array}{*{20}c} {{\rm CF}_{\rm 3} + {\rm NH}_{\rm 3} \to {\rm CF}_3 {\rm H} + {\rm NH}_2 } \\ {2{\rm CF}_3 \to {\rm C}_2 {\rm F}_6 } \\\end{array}$\end{document} and curvature of the Arrhenius plot at high and low temperatures suggests that there are additional sources of fluoroform.
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  • 28
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    New York, NY : Wiley-Blackwell
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 29
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A simple electrostatic model of point dipoles is used which permits direct calculation of the activation energies for the addition of the molecules H2O, H2S, H3N, and H3P to olefins. These calculated values agree with the known experimental data to within ±2 kcal/mole on the average. It was found that the best fit could be obtained with a polar transition state that corresponded to a reduction in bond order from 1 to ½ for the bond-breaking coordinates and an increase in bond order from 0 to 0.18 for the bond-forming coordinates. The replacement of a hydrogen atom of the species H2O, H2S, H3N, or H3P by a polarizable methyl group is expected to stabilize the charge on the central atoms. The following stabilization energies for the pairs H2O—CH3OH, H2S—CH3SH, H3N—CH3NH2, H3P—CH3PH2 were calculated: -4.8 kcal/mole, -0.7 kcal/mole, -1.9 kcal/mole, -0.8 kcal/mole, respectively.
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  • 30
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Combination reactions of the methyl radical have been studied by following the decay of the absorbance of the methyl radical during the course of the reaction by means of kinetic spectroscopy. The limiting values of the second-order rate constants at high pressure were determined for two reactions at room temperature: \documentclass{article}\pagestyle{empty}\begin{document}$ \begin{array}{*{20}c} {{\rm CH}_{\rm 3} + {\rm CH}_{\rm 3} ( + {\rm M}) \to {\rm CH}_{\rm 3} {\rm CH}_{\rm 3} ( + {\rm M}):k_1 = (2.6 \pm 0.3) \times 10^{10} 1{\rm mole}^{ - {\rm 1}} \sec ^{ - 1} } \\ {{\rm CH}_{\rm 3} + {\rm NO }( + {\rm M}) \to {\rm CH}_{\rm 3} {\rm NO }( + {\rm M}):k_2 = (2.4 \pm 0.2) \times 10^9 1{\rm mole}^{ - {\rm 1}} \sec ^{ - 1} } \\ \end{array} $\end{document} The extinction coefficient of the methyl radical was found to have a maximum value of (1.02 ± 0.06) X 104 1 mole-1 cm-1 at 216.4 nm. Integration of the extinction coefficient over the absorption band of the methyl radical gave an oscillator strength of 1.0 X 10-2.
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  • 31
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    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 32
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The vibrationally excited molecules CF3CH3* and CF3CD3* have been synthesized by radical combination (produced by ketone photolysis), and HF and DF elimination from them studied as a function of temperature and pressure. Using RRK theory many calculations have recently been made of critical energies for the decomposition of "hot" fluoroethane molecules. Taking CF3CH3* as an example, it is concluded that the empiricism involved in such calculations renders results of doubtful significance. The non-equilibrium kinetic isotope effect is kH/kD = 3.1 at 470°K. Arrhenius parameters are also presented for radical abstraction reactions from the ketone source molecules.
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  • 33
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the nitric oxide catalyzed, homogeneous, gas-phase isomerization of 1,trans-3,trans-5-heptatriene have been studied for temperatures ranging between 130°C and 241°C. The very clean reaction involves exclusive geometrical isomerization about the 5,6-π-bond. The observed rate constants for \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm NO} + trans - {\rm 3,}trans{\rm - 5}\stackrel{1}{\rightarrow}trans - 3,cis - 5 + {\rm NO} $\end{document} can be represented (with standard errors) by log k1 = (7.18 ± 0.06) - (16.75 ± 0.12)/θ, where θ = 2.303 RT in kcal/mole. The consecutive-step reaction mechanism involves addition of NO to the double bond (Ka, b = ka/kb), followed by rotation of the 5,6-C—C bond in the adduct radical (kc.)Analysis of the observed activation parameters shows, that kc is rate-controlling and consequently k1 = kcKa, b. Estimates of kc and Ka, b lead to a value of k1 in good agreement with experiment.Comparing our data with those previously obtained for the similar 1,3-pentadiene system results in a value for the extra stabilization energy generated in the 1,3-heptadienyl radical of 18.5 ± 1.7 kcal/mole. This value is discussed in view of comparable data in the literature.
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  • 34
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    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Arrhenius parameters have been measured for the abstraction of hydrogen from the C Si, Ge, and Sn tetramethyls: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {k({\rm ml m}^{ - {\rm 1}} {\rm s}^{ - {\rm 1}} )} \hfill & {{\rm for}} \hfill & {{\rm C}({\rm CH}_{\rm 3} )_4 = {{10^{12.0} {\rm e}^{ - 8370} } \mathord{\left/ {\vphantom {{10^{12.0} {\rm e}^{ - 8370} } {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \hfill \\ {k({\rm ml m}^{ - {\rm 1}} {\rm s}^{ - {\rm 1}} )} \hfill & {{\rm for}} \hfill & {{\rm Si(CH}_{\rm 3} {\rm )}_{\rm 4} = {{10^{11.9} {\rm e}^{ - 7300} } \mathord{\left/ {\vphantom {{10^{11.9} {\rm e}^{ - 7300} } {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \hfill \\ {k({\rm ml m}^{ - {\rm 1}} {\rm s}^{ - {\rm 1}} )} \hfill & {{\rm for}} \hfill & {{\rm Ge(CH}_{\rm 3} {\rm )}_{\rm 4} = {{10^{11.7} {\rm e}^{ - 7370} } \mathord{\left/ {\vphantom {{10^{11.7} {\rm e}^{ - 7370} } {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \hfill \\ {k({\rm ml m}^{ - {\rm 1}} {\rm s}^{ - {\rm 1}} )} \hfill & {{\rm for}} \hfill & {{\rm Sn(CH}_{\rm 3} {\rm )}_{\rm 4} = {{10^{11.7} {\rm e}^{ - 7250} } \mathord{\left/ {\vphantom {{10^{11.7} {\rm e}^{ - 7250} } {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \hfill \\ \end{array} $$\end{document} The rate constants correlate with the proton chemical shift, which is related to a polar effect. In all cases except carbon, a hot-molecule β-fluorine rearrangement-elimination reaction occurs following radical combination: \documentclass{article}\pagestyle{empty}\begin{document} $$ ({\rm CF}_3 {\rm CH}_2 {\rm M}({\rm CH}_3 )_3 )^* \to {\rm CF}_2 {\rm CH}_2 + {\rm FM}({\rm CH}_3 )_3 $$ \end{document} We suggest the occurrence of a radical exchange reaction for the Si, Sn, and Ge systems, \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CF}_3 + {\rm M}({\rm CH}_3 )_4 \rightleftharpoons{\rm CF}_3 {\rm M}({\rm CH}_3 )_4 \to {\rm CH}_3 + {\rm CF}_3 {\rm M}({\rm C}{\rm H}_3 )_3 $$\end{document} with kexchange (CF3 + Sn(Me)4) ∼ 107 ml m-1 s-1.
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  • 35
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 36
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A check of the data from comparative rate single-pulse shock tube experiments have been carried out through the use of a new standard reaction, the decyclization reaction of ethylcyclobutane. The rate expressions for cyclohexene and 2,2,3-trimethylbutane have been found to be \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} k({\rm C}_{\rm 6} {\rm H}_{{\rm 10}} \to 1,3 - {\rm C}_4 {\rm H}_6 + {\rm C}_2 {\rm H}_4 ) = 10^{15.3} \exp ( - 33,690/T)\sec ^{ - 1} ,950^ \circ - 1100^ \circ {\rm K,2} - {\rm 6atm} \\ k(t{\rm C}_4 {\rm H}_9 - {\rm iC}_3 {\rm H}_7 \to t{\rm C}_{\rm 4} {\rm H}_{\rm 9} \cdot + {\rm iC}_{\rm 3} {\rm H}_7 \cdot ) = 10^{16.5} {{\exp ( - 36,830} \mathord{\left/ {\vphantom {{\exp ( - 36,830} T}} \right. \kern-\nulldelimiterspace} T})\sec ^{ - 1} ,1000^ \circ - 1100^ \circ {\rm K,2} - {\rm 6atm} \\ \end{array} $$\end{document} in excellent agreement with previously published results. Most of the small discrepancy that does exist is apparently due to the differences between the present and earlier (decomposition of isopropyl bromide) "standard" reaction. For the latter process, the present study yields \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm iC}_{\rm 3} {\rm H}_7 {\rm Br} \to {\rm C}_{\rm 3} {\rm H}_6 + {\rm HBr}) \to 10^{13.73} {\rm exp(}{{ - 23,970} \mathord{\left/ {\vphantom {{ - 23,970} {T\sec ^{ - 1} ,800^ \circ - 1000^ \circ {\rm K,2} - {\rm 6}}}} \right. \kern-\nulldelimiterspace} {T\sec ^{ - 1} ,800^ \circ - 1000^ \circ {\rm K,2} - {\rm 6}}}{\rm atm)} $$\end{document} These results confirm the correctness of previously published comparative rate single-pulse shock tube experiments. They demonstrate once again that for the decomposition of paraffin hydrocarbons, calculated preexponential factors are at least an order of magnitude higher than the directly measured number and that the accepted value of the heat of formation of t-butyl radicals ΔHf300(tC4H9·) = 29 kJ (6.8 kcals) is at least 10 kJ too low. Finally, attention is called to recent studies on neopentane decomposition in flow and static systems which are in complete agreement with the present conclusions.
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  • 37
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 38
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The competitive reactions of Br atoms with CH4 and CD4 were studied over the temperature range of 562° to 637°K. Over this temperature interval, the kinetic isotope effect, kH/kD, varied from 3.05 to 2.47 for the reactions \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm Br} + {\rm CH}_{\rm 4} \stackrel{k_H}{\rightarrow}{\rm HBr} + {\rm CH}_3 } \\ {{\rm Br} + {\rm CD}_{\rm 4} \stackrel{k_D}{\rightarrow}{\rm DBr} + {\rm CD}_3 } \\ \end{array} $$\end{document} The rate constant ratio kH/kD, expressed in Arrhenius form, was found to equal (1.10 ± 0.05) exp (1030 ± 60/RT). A comparison is presented between the experimental result and the result obtained theoretically from absolute rate theory using the London-Eyring-Polanyi-Sato (LEPS) method of constructing the potential energy surface of the reaction. The agreement between theory and experiment is very poor, and this is believed to arise from the highly unsymmetrical nature of the potential energy surface involved in these reactions. A comparison is also presented between the kH/kD values obtained in the Br + CH4-CD4 experiments and the available data on the corresponding Cl + CH4-CD4 reactions.
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  • 39
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    ISSN: 0538-8068
    Keywords: Chemistry ; Physics Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 40
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 41
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Information on physical and chemical properties, especially on the structure and chemical bonding of M[FeCl4]-complexes has been obtained by measurements of the optical absorption, the MÖSSBAUER effect and EPR. (M stands for a monovalent cation.) The iron(III) chlorocomplex compounds Ag[FeCl4], Rb[FeCl4] and Li[FeCl4] have been proved to exist within the systems MCl—FeCl3 by measurements of optical spectra and EPR.
    Notes: Durch optische Absorptionsmessungen, MÖSSBAUER- und EPR-Untersuchungen werden Ergebnisse über die physikalischen und chemischen Eigenschaften, die Struktur und die Bindungsverhältnisse in M[FeCl4]-Komplexen erhalten. Bei diesen Untersuchungen konnten die Komplexverbindungen Ag[FeCl4], Rb[FeCl4] und Li[FeCl4] mittels einer EPR-Methode bzw. optischer Absorptionsmessungen nachgewiesen werden.
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  • 42
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: By electrolytical reduction of solutions of TiCl4 in methanol blue solutions of TiCl3 were obtained from which the crystalline adducts TiCl3 · 4 CH3OH and TiCl3 · 5 CH3OH were isolated. These solids were used as starting material for the preparation of other TiCl3 complexes. By exchange of ligands blue TiCl3 · 3 DMF was obtained which in vacuo could be thermally decomposed to green TiCl3 · 2 DMF. The thermal decomposition of TiCl3 · 3 THF was newly studied. Magnetic susceptibilities, infrared and electron spectra were measured.
    Notes: Durch elektrolytische Reduktion von TiCl4 in Methanol wurden blaue TiCl3-Lösungen erhalten, aus denen die kristallinen Addukte TiCl3 · 4 CH3OH und TiCl3 · 5 CH3OH isoliert werden konnten. Diese dienten als Ausgangsmaterial zur Präparation anderer TiCl3-Komplexe. Durch Ligandenaustausch wurde blaues TiCl3 · 3 DMF erhalten, das sich im Vakuum thermisch zu grünem TiCl3 · 2 DMF abbauen ließ (DMF = Dimethylformamid). Der thermische Abbau von TiCl3 · 3 THF wurde neu untersucht. Magnetische Suszeptibilitäten, Infrarot- und Elektronenspektren wurden gemessen.
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  • 43
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Complexes of the formula Cu2X3 (OR)(N∩N)2 [X = Cl, Br; R = H, CH3; N∩N = bidentate amineligand] are described, their magnetic and spectrophotometric properties are discussed and the possible structures deduced.
    Notes: Es werden Komplexe der Bruttozusammensetzung Cu2X3(OR) (N∩N)2 [X = Cl, Br; R = H, CH3; N∩N = zweizähliger Aminligand] beschrieben, ihr magnetisches und spektrales Verhalten diskutiert und mögliche Strukturen abgeleitet.
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  • 44
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 372 (1970), S. 106-112 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The systems LaP/P and CeP/P were investigated. Polyphosphide phases with the compositions LaP1.6-2.5 (A), LaP3.5-5.3(B), LaP5.8-9.0(C) and LaP6.5-8.9(D), respectively, as well as CeP1.7-2.4 (A′), CeP3.5-6.5(B) CeP6.5-9.0(C) and were found. The phases B and C of lanthanum and cerium are isotypic, but not the phases A and A′. The phases C and D of lanthanum are different modifications with approximately equal homogenity ranges.
    Notes: Es wurden die Systeme LaP/P und CeP/P untersucht. Dabei wurden Polyphosphidphasen der Zusammensetzung LaP1,6-2,5 (A), LaP3,5-5,3 (B) LaP 5,8-9,0 (C) bzw. LaP6,5-8,9 (D), sowie CeP1,7—2,4 (A′), CeP3,5-6,5 (B) und CeP6,5-9,0(C) gefunden. Die Phasen B und C beim Lanthan und Cer sind isotyp, dagegen nicht die Phasen A und A′. Die Phasen C und D beim Lanthan sind verschiedene Modifikationen mit annähernd gleichem Homogenitätsbereich.
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  • 45
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 372 (1970), S. 119-126 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: For the alkali fluorosulfates MSO3F infrared spectra (M = Li, Na, K, Rb, Cs) and also RAMAN spectra (M = K, Rb, Cs) have been recorded. The results are discussed to get some information about the lattice structures. The C3 axis of the anion has several possibilities of orientation in the unit cell for the salts with heavy cations.
    Notes: Die Infrarotspektren der Alkalifluorosulfate MSO3F sowie die Raman-Streuung für M = K, Rb und Cs wurden aufgenommen. Die Ergebnisse werden diskutiert und zu einigen Aussagen über die Gitterstrukturen benützt. Die dreizählige Achse des Anions bei den schwereren Salzen besitzt mehrere Orientierungsmöglichkeiten in der Einheitszelle.
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  • 46
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 372 (1970), S. 134-143 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The stability constants of the copper complexes of acetoacetdialkylamides and substituted acetoacetanilides have been determined by potentiometric pH-measurements. The variation of stability constants with phenyl substituents is interpreted.
    Notes: Die Stabilitätskonstanten der Kupferchelate von Acetessigsäuredialkylamiden und substituierten Acetessigsäureaniliden wurden durch potentiometrische Bestimmung der Wasserstoffionenkonzentration ermittelt. Der Einfluß der Substituenten am Phenylring auf die Stabilität der Komplexe wird durch induktive, mesomere und sterische Effekte erklärt. Die größere Stabilität der Kupferkomplexe mit Acetessigsäuredialkylamiden wird darauf zurückgeführt, daß die Resonanz des Chelatringsystems nicht wie bei den Acetessigsäureaniliden durch ein zweites Resonanzsystem gestört wird.
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  • 47
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The stability constants of the copper complexes of acetoacet-2-amidopyridine and-2-amidopyrimidine have been determined by potentiometric pH-measurements. The variation of stability constants with pyridyl and pyrimidyl substituents is interpreted.
    Notes: Die Stabilitätskonstanten der Kupferchelate von Acetessigsäure-2-amidopyridinen und -pyrimidinen werden durch potentiometrische Bestimmung der Wasserstoffionenkonzentration ermittelt, Der Einfluß der Substituenten am Pyridin- bzw. Pyrimidinring wird diskutiert und die Abstufung der Komplexstabilitäten durch die unterschiedliche Konjugation des π-Elektronensystems des Rings mit dem Chelatringsystem erklärt.
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  • 48
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: This paper contains: 1The synthesis of the 1.3-disilacyclopentenes (a)(b)(2) and of the 1.3-disilacyclo-butane (c); formulas see above.2The synthesis of the 1.3-disilacyclopentane skeleton (d) and of the SiCl-functional derivatives (e) (f ) (g) (h) (i) as well as of SiH-containing derivatives, e.g. (j).3The chlorination of (i) with SO2,Cl2, yielding (k) and (l), and the formation of (m) from (k) with K-methypyrrolidine.4The synthesis of the spirane (n).5The synthesis of the ten-membered ring(o) and of the unsaturated derivatives (p)and (q). Besides the synthetic routes, spectroscopic data (ir, pmr, and mass spectra) of the cyclic compounds as well as of the intermediate products are given.
    Notes: Es wird berichtet über: 1Die Synthese der 1,3-disilacyclopentene (a) (b)2 und des 1,3-disila-cyclobutans (c) 2Die Synthese des 1,3-Disilacyclopentan-Gerüstes (d) und der SiCl-funktionellen Derivate (e)(f)(g)(h)(i)sowie der SiH haltigen Derivate, z. B. (j) 3Die Chlorierung von (i) mit SO2Cl2 zu (k) und (1) und die Bildung ron (m) aus (k) mit K-Methylpyrrolidin 4Die Synthese des Spirans (n) 5Die Synthese des 10-Ringes (o) und der nngesattigten Derivate (p) und (q). SeFen den Synthesewegen werden spelitroskopische Daten und PMR-Spektren der cyclischen Verhindungen sou ie der Zwischenprodukte angegeben.
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  • 49
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 372 (1970), S. 74-78 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The phase diagram of the condensed system Br2—N2O4 has been reinvestigated with increased accuracy. The results of this study and comparison with the melting points of NO2F and NO2Cl lead to a new interpretation of the observable unstable state. It seems to indicate N2O4-rich mixed crystals or some metastable modification of N2O4 rather than an eutectic NO2Br—N2O4.
    Notes: Für das kondensierte System Br2—N2O4 wurde das Zustandsdiagramm erneut and mit erhöhter Genauigkeit untersucht. Das Ergebnis dieser Untersuchung und ein Vergleich mit den Schmelzpunkten von NO2F und NO2Cl führen zu einer neuen Deutung des beobachtbaren instabilen Zustandes. Dieser Zustand scheint eher anf N2O4-reiche Mischkristalle oder eine instabile N2O4-Modifikation hinzuweisen als auf ein Eutektikum NO2Br—N2O4.
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  • 50
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of phosphobenzene (phenylpolyphosphine A) with various amounts of phenyllithium give l,4-dilithio-l,2,3,4-tetraphenyl-tetraphosphine, tetraphenyldiphosphine, l,3-dilithio-l,2,3-triphenyltriphosphine, 1-lithio-l,2,2-triphenyl-diphosphine, 1,2-dilithio-diphenyldiphosphine and, after cleavage of all P—P bonds, lithium-diphenylphosphide, dilithio-phenylphosphide and triphenylphosphine. Formation and reactions of the products are discussed.
    Notes: Reaktionen von Phenylpolyphosphin A mit kleinen Mengen Lithiumphenyl führen zunächst zu 1,4-Dilithium-l,2,3,4-tetraphenyl-tetraphosphin, Tetraphenylbiphosphin und 1-Lithium-l,2,2-triphenyl-biphosphin. Durch schrittweise Erhöhung der LiC6H5-Konzentration können als weitere Zwischenprodukte 1,3-Dilithium-1,2,3-triphenyl-triphosphin und 1,2-Dilithium-diphenyl-biphosphin nachgewiesen werden. Nach Spaltung aller P—P-Bindungen liegen neben dem Hauptprodukt Lithium-diphenyl-phosphid wenig Dilithium-phenylphosphid und Triphenylphosphin vor. Bildung und Umsetzung der Substanzen werden durch Aufstellung einer Reihe abnehmenden elektrophilen Verhaltens interpretiert.
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  • 51
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 372 (1970), S. 87-99 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The crystal structures of BaSi2, SrSi2 and of a new modification of CaSi2 are described. The Si arrangements in these structures are discussed. There are Si4 tetrahedrons in BaSi2, a Sin threedimensional framework in SrSi2 and twodimensional corrugated sheets of Si hexagons in CaSi2.
    Notes: Die Kristallstrukturen von BaSi2 und SrSi2 werden beschrieben. Von CaSi2 wurde eine neue Modifikation aufgefunden. Die in den 3 Phasen nachgewiesenen Si-Verbände (Si4-Tetraeder im BaSi2, Sin-Raumnetzgerüst im SrSi2 und Sin-Schichten im CaSi2) werden vergleichend diskutiert.
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  • 52
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 53
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The electronic absorption spectra of the ions PS43-, AsS43- and SbS43- have been measured in aqueous solution. The transitions are assigned and discussed, using a simple MO diagram.
    Notes: Es wurden die Elektronenspektren von PS43-, AsS43- und SbS43- in wäßriger Lösung gemessen. Alle Ionen weisen unterhalb von 54 kK lediglich eine starke Bande auf. Die Banden werden an Hand eines stark vereinfachten MO-Schemas zugeordnet. Es läßt sich zeigen, daß bei den oben erwähnten Ionen praktisch keine π-Bindungen vorliegen.
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  • 54
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Sodium bromite may be prepared by dismutation of hypobromite solution produced by the addition of bromine to concentrated caustic soda at 0 °C, the hypobromite being destroyed after the maximum bromite concentration has been reached. Using bromine water or bromine vapour diluted by nitrogen at low temperatures, it is possible to prepare bromite-free hypobromite solutions.
    Notes: Eine aus Brom und Natronlauge hergestellte Natriumhypobromitlösung wird zur Darstellung des Natriumbromits durch Disproportionierung benutzt. Das im Maximum der Bromitkonzentration vorhandene Hypobromit muß zerstört werden.Mit Bromwasser oder stickstoffverdünnten Bromdämpfen kann bei niedrigen Temperaturen eine bromitfreie Hypobromitlösung hergestellt werden.
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  • 55
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 372 (1970), S. 150-161 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The crystal structure of CuBr · (C2H5)4P2 has been determined by single crystal X-ray methods. The crystals are triclinic (space group P 1) with two formula units per unit cell (a) = 9,29, b = 9,92, c = 7,57 Å, α = 85,3°, β = 106,6°, γ = 109,1°. The copper atoms are tetrahedrally coordinated by two bromine and two phosphorus atoms (of different biphosphine molecules). The structure has continuous chains running parallel c, in which the copper atoms are linked together by alternating double bridges consisting of two biphosphine molecules and two bromine atoms, respectively.
    Notes: Die Kristallstruktur von CuBr · (C2H5)4P2 wurde röntgenographisch aus Einkristallaufnahmen bestimmt. Die Verbindung kristallisiert in der Raumgruppe P 1 mit den Gitterkonstanten a = 9,29 Å, b = 9,92 Å, c = 7,57 Å, α = 85,3°, β = 106,6°, γ = 109,1° und 2 Formeleinheiten in der Elementarzelle. Die Cu-Atome besitzen tetraedrische Umgebung und werden abwechselnd über Doppelbrücken aus 2 Bromatomen bzw. 2 Biphosphinmolekülen miteinander verknüpft, auf diese Weise entstehen unendliche Ketten parallel der c-Achse.
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  • 56
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The influence of sulphur containing substances on the formation of iron, molybdenum and nickel carbonyl has been investigated. Under tribomechanical treatment, these reactions proceed already at normal conditions, sulphur and S-containing compounds catalysing the carbonylisation. This sensibilisation effect is due according to kinetical and thermodynamical measurements- to the formation of S-containing intermediates, lowering the apparent activation energy of the nickel carbonyl formation from 13.1 to 6.4 kcals/mole. The influence of H2S on the carbonylisation of industrial products was studied.
    Notes: Es wurde der Einfluß schwefelhaltiger Substanzen auf die Bildung von Eisen-, Molybdän- und Nickelcarbonyl untersucht. Unter Bedingungen der tribomechanischen Bearbeitung verlaufen diese Reaktionen bereits unter Normalbedingungen, wobei Schwefel und schwefelhaltige Verbindungen die Carbonylisierung dor Metalle katalytisch beschleunigen. Nach kinetischen und thermodynamischen Messungen beruht der sensibilisierende Effekt auf der Bildung von schwefelhaltigen Zwischenverbindungen, unter deren Mitwirkung für die Nickelcarbonylbildung die scheinbare Aktivierungsenergie der Reaktion von 13,1 auf 6,4 kcal/mol sinkt. Der sensibilisierende Einfluß von H2S auf die Carbonylisierung technischer Produkte wurde untersucht.
    Additional Material: 7 Ill.
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  • 57
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Adsorption of various acids on anatase of high surface area was studied. Phosphoric, arsenic, sulphuric and acetic acid are specifically adsorbed; hydrochloric and perchloric acid are not adsorbed. Phosphate ions are bound on the TiO2 surface also from NaH2PO4 and Na2HPO4 solutions; sodium ions are adsorbed at the same time. OH- ions on the surface are replaced by anions such as H2PO4- in these reactions. The bonding of adsorbed phosphate ions is not purely ionic. Infrared spectra show that adsorbed acetic acid is bound as acetate. NO2 reacts with the basic OH- ions undergoing disproportionation; OH- ions are replaced by NO3- ions.Phophoric acid adsorption corresponded always to half the total OH population on five different TiO2 samples. The TiO2 surface is not completely covered by OH groups. The maximum coverage is ca. 7.5 μMol OH/m2.
    Notes: Die Adsorption verschiedener Säuren an einem feinteiligen Anatas wurde untersucht. Vor allem Phosphorsäure, Arsensäure, Schwefelsäure und Essigsäure werden spezifisch adsorbiert. Salzsäure und Perchlorsäure werden nicht adsorbiert. Phosphat-Ionen werden auch aus NaH2PO4- und Na2HPO4 -Lösung gebunden; zugleich werden Natriumionen adsorbiert. Bei diesen Reaktionen werden OH- -Ionen der TiO2-Oberfläche durch Anionen, z. B. H2PO4--Ionen, ersetzt. Die Bindung der adsorbierten H2PO4--Ionen ist nicht rein ionisch. Adsorbierte Essigsäure liegt als Acetat vor, wir das Infrarotspektrum zeigt. NO2 reagiert mit den basischen OH--Ionen der Oberfläche unter Disproportionierung; dabei werden die OH--Ionen durch NO3- ersetzt.Bei fünf untersuchten TiO2 -Präparaten entspricht die Phosphorsäure- Adsorption jeweils der Hälfte des gesamten Gehaltes an OH-Gruppen. Nur ein Teil deer Oberfläche ist mit OH-Gruppen belegt. Die maximale Belegungsdichte beträgt etwa 7,5 μMol OH/m2.
    Additional Material: 6 Ill.
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  • 58
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The ternary disilicides of group-II elements Ca1-xSrxSi2 und Sr1-xBaxSi2 are prepared and crystallographically investigated. In the quasibinary system CaSi2—SrSi2 the structures of the Ca-rich phases can be described as stacks of twodimensional corrugated sheets of Si hexagons. The phases Sr1-xBaxSi2 with X = 0.2 to X = 1.0 crystallize in the structure type of BaSi2 with isolated Si4 tetrahedrons. There in no miscibility between CaSi2 and BaSi2 in the solid phase.
    Notes: Die ternären Erdalkalidisilicide der Stöchiometrie Ca1-xSrxSi2 und Sr1-xBaxSi2 wurden dargestellt und röntgenographisch charakterisiert. Im quasibinären Schnitt CaSi2—SrSi2 wurden im Ca-reichen Teil Phasen erhalten, deren Strukturen sich als Stapelvarianten mit zweidimensionalen, gewellten Si-Sechsecknetzen erwiesen. Im System Sr1-xBaxSi2 tritt der Strukturtyp des BaSi2 mit isolierten Si4-Tetraedern von x = 0,2 bis x = 1,0 auf. Der quasibinäre Schnitt BaSi2—CaSi2 entspricht dem Zustandsdiagramm eines Zweistoffsystems ohne Mischkristallbildung.
    Additional Material: 4 Ill.
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  • 59
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Durch Umsetzung von zinkacetylacetonat mit substituierten Pyridinen und Chinolinen wurden elf Neutralkomplexe mit Fünferkoordination, [Zn(acac)2L], dargestellt.
    Notes: Zinc acetylacetonate was reacted in methanolic medium with substituted pyridines and quinolines, and eleven non-electrolytic, pentacoordinated mixed-ligand complexes [Zn(acac)2L] have been isolated and characterised. The infra-red spectra indicate the presence of both acetylacetone and the bonded ligand.
    Additional Material: 2 Tab.
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  • 60
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 61
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Es wurde die Substitution von Halogenid durch Hydroxid bei einigen Halogenopentamminkobalt(III)- und -chrom(III)-Kationen in wäßrigem Dioxan bei Alkalikonzentrationen bis zu 0.1 M untersucht. Bei überschüssigem OH- (konstante Ionenstärke) wurden Geschwindigkeitskonstanten nach scheinbar erster Ordnung ermittelt. Es ist eine dem Gleichgewicht vorgelagerte Ionenpaar-Assoziation angezeigt, wobei aber nicht über die Art der Weiterreaktion des Ionenpaares - Direktaustausch oder Protonenabzug - entschieden werden kann. Bei CoIII ist die Ionenpaarbildung Stärker als bei CrIII; sie nimmt mit steigendem Dioxangehalt zu.
    Notes: The replacement, by hydroxide ion, of the coordinated halide from some halogenopentamminecobalt(III) and -Chromium(III) cations in aqueous dioxan has been studied over a range of alkali concentrations up to 0.1 M. With excess of hydroxide ion at constant ionic strength, pseudo first-order rate constants were obtained. The results support a pre-equilibrium association of complex and hydroxide ions in these media, but do not provide distinction as to whether the resulting ion-pair subsequently reacts by direct exchange or by proton removal. The extents of ion association are found to be greater for the cobalt(III) than for the chromium(III) system, increasing with the amount of dioxin in the solvent mixture.
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  • 62
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Single crystals of the system CdCr2(S1-xSex)4 have been prepared by chemical transport with I2/AlCl3 mixtures and by flux growth from solutions in molten CdCl2.
    Notes: Im System CdCr2(S1-xSex)4 wurden Einkristalle durch Transportreaktion mit J2/AlCl3-Gemischen als Transportmittel und durch Kristallisation aus CdCl2-Schmelzlösungen hergestellt.
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  • 63
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 64
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The transformation of vapour-deposited α-CuPc films into the β-phase, occuring when the films are heat-treated, is investigated by means of IR spectroscopy. X-ray diffraction and electron microscopy. The absorbance at 783 cm-1 provids us an useful measure for the degree of transformation, whereas in some cases results of the X-ray diffraction where not unequivocal. The transformation starts between 185 und 216°C, depending on the temperature of the substrate during the preparation of the films. Films deposited onto substrates below -35°C proved to be amorphous. They can be crystallized at temperatures below the α-β-transformation point.
    Notes: Die thermische Umlagerung von α-CuPe-Aufdampfschichten in die β-Form wird IR-spektroskopisch, röntgenographisch und elektronenmikroskopisch verfolgt. Quantitative Aussagen über den Umwandlungsgrad folgen mit befriedigender Genauigkeit aus der (normierten) Extinktion der IR-Bande bei 783 cm-1, während die Röntgenstreukurven bei Aufdampfschichten z.T. keine befriedigenden Ergebnisse liefern. Der Beginn der Umwandlung wurde bei Temperaturen zwischen 185 und 216°C beobachtet und hängt von der Substrattemperatur bei der Herstellung der Schicht ab. Schichten, die auf Substrate von Temperaturen unter -35°C sublimiert wurden, erwiesen sich als röntgenamorph. Sie kristallisieren beim Tempern unterhalb der α-β-Umwandlungstemperatur.
    Additional Material: 7 Ill.
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  • 65
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Mono- and binuclear carbonyls of 5th, 6th and 8th group transition metals react with organosulfonyl chlorides, RSO2Cl, to form organosulfinato metal chlorides with, in the case of electronegative R (R = CF3), metal(II) and, in the case of electropositive (R = p-CH3C6H4), metal(II) or (III). Bis(organosulfinato) complexes are obtainable from metal(II) chlorides and sodium organosulfinates.In all these new sulfinato compounds the ligand is bound to the metal through both its oxygen atoms; this is deduced from the IR spectra.
    Notes: Durch Umsetzung von ein- oder zweikernigen Metallcarbonylen der 5.,6. und 8. Nebengruppe mit Organosulfonylchloriden, RSO2Cl, erhält man bei elektronegativem R (R = CF3) durchwegs Organo-doppel-O-sulfinato-metallchloride mit zweiwertigem Metall. Bei elektropositiveren organischen Resten (R = p·CH3C6H4) entstehen in Abhängigkeit von der Oxydierbarkeit des betreffenden Metallcarbonyls ebenfalls Organo-doppel-O-sulfinato-metallchloride mit zwei- oder dreiwertigem Metall.Bis(organosulfinato)-Komplexe, in denen die Liganden gleichfalls über beide O-Atome an das Metall geknüpft sind, werden prinzipiell durch Reaktion von Metall(II)-chloriden mit Natriumorganosulfinaten dargestellt.Die O-Sulfinato-Verknüpfung aller hier neu beschriebenen Verbindungen geht aus den IR-Spektren hervor.
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  • 66
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 373 (1970), S. 168-175 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The compounds LaSF, CeSF, EuSF and LaSeF were prepared by reaction of the sesquichalcogenides with the fluorides. The sulphidefluorides crystallize with the PbFCl structure, while LaSeF crystallizes with an unknown orthorhombic structure.
    Notes: Durch Umsetzung der Chalkogenide mit den entsprechenden Fluoriden wurden die Verbindungen LaSF, CeSF, EuSF, und LaSeF erhalten. Die Sulfidfluoride kristallisieren im PbFCl-Typ, LaSeF orthorhombisch in einer bisher nicht bekannten Struktur.
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  • 67
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 373 (1970), S. 182-188 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: By the reduction of C3F7Fe(CO)4J with sodium borohydride in methanol a solution is obtained from which derivatives of the very unstable perfluoropropyliron tetracarbonyl hydride C3F7Fe(CO)4H can be precipitated. The compounds [C3F7Fe(CO)4]2Hg and [C3F7Fe(CO)4]2[Fe(N2C12H8)3] have been characterized by their IR, NMR and mass spectra.
    Notes: Durch Reduktion einer Lösung von Heptafluor-n-propyl-eisen-tetracarbonyljodid, C3F7Fe(CO)4J, in Methanol mittels Natriumboranats entsteht eine Lösung, aus der Quecksilbercyanid und Tri-o-phenanthrolin-eisen(II)-sulfat Derivate des Heptafluor-n-propyl-eisentetracarbonylwasserstoffs, [C3F7Fe(CO)4]2Hg und [C3F7Fe(CO)(4)]2[Fe(N2C12H8)3] ausfällen. Aus dem Phenanthrolinderivat kann mittels Phosphorsäure das äußerst zersetzliche Carbonylhydrid C3F7Fe(CO)4H in Freiheit gesetzt werden. Die beiden beständigen Verbindungen sind durch IR-, NMR- und Massenspektren charakterisiert worden.
    Additional Material: 3 Tab.
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  • 68
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 373 (1970), S. 198-203 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: LiHC2O4 · H2O crystallizes in space group P 1 with a0 = 4.99, b0 = 6.16, c0 = 3.45 Å; α0 = 96.3°, β0 = 98.0°, γ0 = 80.4° and Z = 1. The crystal structure has been determined by direct methods. Refinement by least squares methods resulted to R1 = 8,3%. In the structure the oxalate group is not planar. The angle between the two O—C—O planes is 2.9°.
    Notes: LiHC2O4 · H2O kristallisiert in der Raumgruppe P 1 mit a0 = 4,99, b0 = 6,16, c0 = 3,45 Å; α0 = 96,3°, β0 = 98,0°, γ0 = 80,4° und Z = 1. Die Kristallstruktur wurde mit direkten Methoden bestimmt. Die Verfeinerung der Parameter nach der Methode der kleinsten Quadrate ergab einen R1-Wert von 8,3%. Die Oxalatgruppe ist in der Struktur nicht eben. Der Winkel zwischen den beiden O—C—O-Ebenen beträgt 2,9°.
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