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1.
Processes of direct and electrocatalytic (in the presence of electrochemically reduced Cp2TiCl2) reduction of three α-bromoketones containing the C(sp3)-Br or C(sp2)-Br bond, viz., 2-bromo-and 2,6-dibromo-4,4-dimethylcyclohexa-2,5-dien-1-ones and α-bromo-acetophenone, were studied by cyclic voltammetry
and preparative electrolysis. In all cases, the dissociative electron transfer proceeds via the concerted mechanism. Preparative electrolysis of these α-bromoketones in the presence of Cp2TiCl2 affords the reductive debromination products in 40–80% yield at low cathodic potentials (−0.85 V vs. Ag/AgCl/KCl). In the case of 2,6-dibromo-4,4-dimethylcyclohexa-2,5-dien-1-one in the potentiostatic regime, only one bromine
atom can be eliminated selectively.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 977–983, May, 2007. 相似文献
2.
《Journal of Coordination Chemistry》2012,65(1-4):77-89
Abstract A steric effect in the carbon-skeleton rearrangement catalyzed by heptamethyl cobyrinate perchlorate, [Cob(II)7C1ester]C104, was investigated under electrochemical conditions. The controlled-potential electrolyses of alkyl halides having two carboxylic ester groups of different bulkiness on the same carbon atom, such as 2,2-bis(ethoxycarbonyl)-l-bromopropane, l-bromo-2-tert-butoxycarbonyl-2-ethoxy-carbonylpropane, l-bromo-2-cyclohexyloxycarbonyl-2-ethoxycarbonylpropane, and l-bromo-2-ethoxy-carbonyl-2-phenoxycarbonylpropane, were carried out in N,N-dimethylformamide, as catalyzed by [Cob(II)7C1ester]CIO4, to give the corresponding ester-migrated products in the dark at—1.5 V vs SCE in the presence of acetic acid and at—2.0 V vs SCE without acetic acid. As regards a correlation between bulkiness of an ester group and a migration aptitude, a smaller ester group tends to migrate to the adjacent carbon atom more readily than a larger one. The origin of such a steric effect is discussed with attention to the rate-determining step. 相似文献
3.
在综述电化学近50年来比能量提高情况的基础上,讨论了现代科技发展对电池比能量的要求,以及当今电池能在多大程度上满足这些要求,并讨论了进一步提高电池比能量的可能性及可能途径. 相似文献
4.
P. Kränke H. Matschiner R. Trutschel M. Wahren 《Isotopes in environmental and health studies》2013,49(1-2):187-191
Abstract The electrochemical reduction of model carboxylic acid at lead cathodes in deuterated media was studied for potential use in the synthesis of special deuterated compounds. Oxalic acid-d2 in D2O gives good yields of glyoxylic acid-d2. An unexpected large isotope effect of 5.3 ± 1.7 was found in this reaction, leading to significant depletion of deuterium content in the aldehyde group. Benzoic acid-d in CD3OD/diluted D2SO4 yields benzyl alcohol-d, 7,7-d2. The isotope effect of 2.4 ± 1.0 is within the expected range. No deuterium is incorporated into the aromatic nucleus. Essentially unlabelled benzyl alcohol is obtained in CD3OH/dil. H2SO4. 相似文献
5.
Gunther Wittstock 《光学与光电技术》2012,(4):6-11
扫描电化学显微镜是一种扫描探针技术,利用微电极检测发生在固/液、液/液或者气/液界面反应物或者反应产物的连续变化。这里将对该技术原理进行详细说明。过去我们工作主要都集中在固定化酶的活性成像。最近研究的领域开始拓展到与能源转变相关材料上,如染料敏化太阳能电池和(生物)燃料电池的氧气催化还原。起初的尝试已经扩展到如何扩宽研究材料的范围和成像模式的应用范围。扫描电化学显微镜的反馈和产生~收集模式已被用于研究染料敏化太阳能电池半导体/电解质界面的光激发染料阳离子再生过程。现在开始关注更多的与太阳能的再生,燃料电池或染料敏化太阳能电池相关的复杂反应,这些复杂的反应包括外部质量传输过程、内部质量和电荷传输过程、多孔物质反应中心的本身活性等。 相似文献
6.
SERS技术由于具有高灵敏度的表面效应,能够检测吸附在金属表面的单分子层或亚单分子层的分子,并能给出丰富的分子结构信息,因而己被广泛应用于界面科学以及定性和定量分析科学领域之中。本文在制备电化学沉积金纳米薄膜的基础上,利用扫描电镜观察金纳米薄膜的形貌,通过分析对巯基苯甲酸在电化学沉积金膜表面的SERS光谱,研究对巯基苯甲酸在金纳米薄膜表面的吸附方式。由SERS光谱分析,我们推断出对巯基苯甲酸可能通过羧基和S原子共同作用吸附在金纳米颗粒表面,且苯环平面可能与金薄膜表面成一定倾斜角。 相似文献
7.
8.
《Phosphorus, sulfur, and silicon and the related elements》2012,187(2):88-95
AbstractTwo new complexes, [Cu(SPPh3)3]2(PF6)2 (1) and [Ag2(SPPh3)2](PF6)2 (2), were prepared from [M(CH3CN)4](PF6)] (M = Cu and Ag) and triphenylphosphine sulfide ligand (SPPh3). The complexes have been characterized by elemental analysis, and UV-Vis and IR spectroscopies. Single-crystal X-ray structure analyses reveals that complexes 1 and 2 can both be described as a planar triangular configuration. Complex 1 is mononuclear and shows two crystallographically independent and chemically identical [Cu(SPPh3)3]+ cations. In binuclear complex 2, the sulfur atoms in SPPh3 adopt two different coordination modes, namely monodentate and monoatomic bridging. Luminescence properties investigation in solid state show that complex 1 revealed only one emission band at 471 nm (λex = 310 nm), which may be attributed to metal-to-ligand charge-transfer [MLCT]. However, complex 2 had two emission peaks which attributed to π–π* and n–π* transitions. Electrochemical experiment illustrated the complexes 1 and 2 represent irreversible Cu+/Cu2+ or Ag+/Ag pairs, respectively. In vitro antioxidant tests showed that the complex 2 had significant antioxidant activity against hydroxyl radicals. 相似文献
9.
XIE Qing-Ji PANG Xiao-Yong NIE Li-Hua YAO Shou-Zhuo Department of Chemistry Chemical Engineering Hunan University Changsha Hunan China 《中国化学》1994,12(5):425-431
Piezoelectric transmission spectroelectrochemistry (PTSEC), i.e., the combination of electrochemistry and spectroelectrochemistry (SEC) with electrochemical quartz crystal microbalance (EQCM) technique is reported by using a normal piezoelectric quartz crystal (PQC) as an optically-transparent electrode (OTE). A theoretical relationship between the PQC response and the spectroelectrochemical response is derived and used to estimate the apparent molar absorptivity of the absorbing species deposited on the OTE on the PQC surface. The complex of copper with aspartic acid is used to test this new PQC-SEC technique. Results show that the combination of three such diverse techniques provides a very useful methodology for studying electrode processes and electrode surface characteristics in situ. 相似文献
10.
Electroreduction of methacryloylacetone and its FeIII and CuII complexes was studied by cyclic voltammetry and preparative electrolysis on a Hg electrode. The possibility of the electropolymerization of the compounds at highly negative potentials (–2.0 V, vs sce) has been demonstrated. The polymers obtained were characterized by elemental analysis, electronic, IR-, and Mössbauer spectroscopy.For part 36, see Ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 255–261, February, 1994. 相似文献