Formation of Active Catalysts in the System: Chlorocuprates−CCl4−n-C10H22

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• 作者：Elena N. Golubeva ; Dmitry N. Kharitonov ; Dmitry I. Kochubey ; Vladimir N. Ikorskii ; Vladimir V. Kriventsov ; Alexander I. Kokorin ; Julia Stoetsner ; Detlef W. Bahnemann
• 刊名：Journal of Physical Chemistry A
• 出版年：2009
• 出版时间：September 24, 2009
• 年：2009
• 卷：113
• 期：38
• 页码：10219-10223
• 全文大小：146K
• 年卷期：v.113,no.38(September 24, 2009)
• ISSN：1520-5215

文摘

Transformations of anionic Cu^II chlorocomplexes have been studied under conditions of catalytic exchange reactions between carbon tetrachloride and n-alkanes. It was shown that chlorocuprates are just precursors and are easily reduced to the genuine catalysts, that is, to the respective Cu^I complexes. Both the composition and the geometric structure of the precursor (CuCl₄²⁻) and, probably, the active site (CuCl₃²⁻) have been investigated by several techniques (UV−vis spectroscopy, electron spin resonance (ESR), extended X-ray absorption fine structure (EXAFS), X-ray absorption near-edge structure (XANES), and static magnetic measurements). The dependence of the metathesis velocity on the [Cl⁻]/[Cu] ratio was found to exhibit a maximum most likely corresponding to the highest content of trichlorocuprite CuCl₃²⁻.