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91.
The rates of cleavage of some XC6H4CH2SnMe3 bonds by aqueous-methanolic perchloric acid have been measured spectrophotometrically, and the rate of cleavage of the MeSn bonds of PhCH2SnMe3 and Me4Sn by monitoring the methane evolution. The results indicate that for X = H, p-Me, o-Me, p-But, o-, m- and p-F and -Cl, and o-Br, the cleavage of the CH2SnMe3 bond involves attack of the acid at the benzylic atom, and is not much faster than that of the SnMe bonds, but that a mechanism involving ring-protonation is important for X = m-Me, and greatly predominant for X = m-OMe. 相似文献
92.
The reduction of 1,10-phenanthroline-5,6-quinone(I), 5,8-quinolinequinone(II) and 6,7-dichloro-5,8-quinolinequinone(III) was investigated using cyclic voltammetry and coulometry at mercury electrodes and 50% dimethylsulfoxide+water solvent. Each compound is reduced to the corresponding hydroquinone in a diffusion-controlled, reversible two-electron process. The pH-dependence of the reversible potential indicated that the quinone forms were unprotonated, but the hydroquinones could be protonated at the heterocyclic nitrogen atom with pKa = 5.3 for I and 3.5 for III. Careful analysis of the cyclic voltammetric peak shape revealed that the difference between the standard potentials for the introduction of successive electrons, E20 ? E10, was 70 ±20, >100 and 80 ± 20 mV for I–III. Investigation of the pH-dependence of E10 and E20 showed that the pKa of the semiquinone of I was about 8. 相似文献
93.
Takeko Matsumura-Inoue Tomoko Tominaga-Morimoto 《Journal of Electroanalytical Chemistry》1978,93(2):127-139
The electrode reactions of Os(II) complexes with α,α′-bipyridine and o-phenanthroline have been studied in non aqueous solvents. Tris bipyridine and tris phenanthroline complexes of Os(II) give one-step oxidation waves and three-step reduction waves, while bis bipyridine complexes of Os(II) containing py2, en, CN2, Cl2 and Br2 as mixed ligands give one-step oxidation waves and two-step reduction waves. Most of these waves correspond to reversible single electron transfers. It is noticed that the half-wave potentials or the peak potentials of bis bipyridine complexes are shifted to more negative direction than those of the tris complex in both oxidation and reduction processes. This is attributable to less electron with drawing nature of substituted ligands than bipyridine. These potential data, the shifts of E1/2 or Ep from those of tris complexes, and δE*, the potential difference between two consecutive single electron waves, are discussed in terms of molecular orbital scheme. 相似文献
94.
Frank Herwig Köhler Hans Jürgen Kalder Ernst Otto Fischer 《Journal of organometallic chemistry》1975,85(2):C19-C22
Carbon-13 NMR data are reported for trimethyltin derivatives containing ERn groups where E C, Si, Ge, Sn, N, O and S including a series of cyclic amines with ring sizes from three to seven. Coupling constant values for the homologous series of fourth group derivatives give goood correlations with the electronegativity of E. The observation of the two-bond, ¦ 2J(119SnE13C) ¦ couplings only in the derivatives containing bulky R groups is rationalized by a bimolecular exchange of ERn groups in the concentrated solutions studied. 相似文献
95.
Three complexes containing bidentate N-2,3-dimethylphenylglycine, (2,3-HDPG), N-2,4-dimethylphenylglycine, (2,4-HDPG) and N-2-ethylphenylglycine, (2-HEPG) acids have been prepared and characterized. These compounds have the general formula Zn(2,3-DPG)2·2 H2O, Zn(2,4-DPG)2 and Zn(2-EPG)2·2 H2O, respectively. The structure of the complexes as inferred from their chemistries have been found to be compatible with the infrared spectral data. The thermal behaviour of these complexes has been studied from their TG, DTG and DSC diagrams obtained in a dynamic atmosphere of pure air. Heats of dehydration have been calculated from DSC curves. 相似文献
96.
Oxygen reduction on immersed gold electrodes has been studied in Li2CO3 melt under steady-state conditions and by the potential-sweep method. Reaction order measurements have established that the species being reduced is not molecular oxygen, but the peroxide ion. The latter is in chemical equilibrium with molecular oxygen and oxide ions. The rate-determining step is the primary charge transfer where (O?) is a transient species. The exchange current densities and activation energies have been determined. Under conditions where O22? diffusion is not limiting (e.g. meniscus electrodes) the rate of neutralization of oxide by CO2 at the electrode surface is probably rate-determining. 相似文献
97.
The program MINIPOL, designed to run on a desk-computer with 32 kbytes of memory, can calculate the optimum values of overall protonation constants and molar intensities of up to 8 species with composition HXXXLρ, from differential-pulse polarographic data. 相似文献
98.
Several Li+- and Na+-acetonitrile models were derived from ab initio calculations at the counterpoise-corrected MP2/TZV++(d,p) level for distorted ion-(MeCN)n clusters with n=1, 4 and 6. Two different many-body ion-acetonitrile models were constructed: an effective three-body potential for use with the six-site effective pair model of Böhm et al., and an effective polarizable many-body model. The polarizable acetonitrile model used in the latter model is a new empirical model which was also derived in the present paper. Mainly for comparative purposes, two ion-acetonitrile pair potentials were also constructed from the ab initio cluster calculations: one pure pair potential and one effective pair potential. Using all these potential models, MD simulations in the NPT ensemble were performed for the pure acetonitrile liquid and for Li+(MeCN) and Na+(MeCN) solutions with 1 ion in 512 solvent molecules and with a simulation time of at least 120 ps per system. Thermodynamic properties, solvation-shell structure and the self-diffusion coefficient of the ions and of the solvent molecules were calculated and compared between the different models and with experimental data, where available. The Li+ ion is found to be four-coordinated when the new many-body potentials are used, in contrast to the six-coordinated structure obtained for the pure pair and effective pair potentials. The coordination number of Na+ is close to six for all the models derived here, although the coordination number becomes slightly smaller with the many-body potentials. For both ions, the solvent molecules in the first shell point their nitrogen ends towards the cation, while in the second shell the opposite orientation is the most common. 相似文献
99.
The proton NMR spectra of N-[2-pyridyl-N-oxide]-derivatives of primary and secondary ethylamines, containing a substituent R on the C atom bearing the amino function, have been completely analysed in terms of the fundamental NMR parameters. The preferred conformations of the compounds investigated were established by the indications from NOE experiments as well as: (1) the long range coupling across the five bond between the aminic hydrogen and the proton in 4-position of the pyridine-N-oxide ring (5JmH,NH ~ 0·5 c/s), (2) the value of the vicinal coupling constant in the fragment CHNH (3JNHCH ~ 7–9 c/s), (3) the large deshielding (Δτ ~ 1–1·5 ppm) observed for the resonance position of the proton on the asymmetric C atom in secondary amine derivatives with respect to the corresponding primary ones, and (4) the diamagnetic shielding produced on protons in position 3 and 4 of the pyridine-N-oxide ring by different aromatic groups introduced in the R substituent.The NMR data confirmed the preferred rotamers previously suggested on the basis of ORD and CD measurements. 相似文献
100.
The incongruent vaporization reactions of Ta2S and Ta6S have been investigated by mass-loss effusion in the temperature range 1576 to 1902 K. By extrapolation of PS(obs) to equilibrium the enthalpies of the reactions and Ta6S = 6 Ta(s) + S(g) were found to be and , respectively. Comparison between the above values, determined by a 2nd law treatment, and 3rd law values was used to derive fef (“free energy function”) values for Ta and S in the compounds. These postulated fef's, which apply only to the elements as present in the compounds measured, are compared to tabulated quantities for the pure solid elements to provide a criterion for 2nd and 3rd law evaluation. 相似文献