Copper Chloride Catalysis: Do μ4-Oxido Copper Clusters Play a Significant Role?

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• 作者：Sabine Becker ; Maximilian Dürr ; Andreas Miska ; Jonathan Becker ; Christopher Gawlig ; Ulrich Behrens ; Ivana Ivanović-Burmazović ; Siegfried Schindler
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：April 18, 2016
• 年：2016
• 卷：55
• 期：8
• 页码：3759-3766
• 全文大小：412K
• 年卷期：0
• ISSN：1520-510X

文摘

Copper chloride catalysis is a well-established field in organic and inorganic chemistry. However, in most cases a detailed mechanistic understanding of the individual reaction steps and identification of reactive intermediates are still missing. The present study reports the results of spectroscopic and spectrometric measurements that support formation of copper agglomerates during catalytic processes. The composition of CuCl₂·2H₂O in several coordinating solvents and the influence of basic coreagents such as NaO^tBu and K₂CO₃ on the structure in the solid state as well as in solution were investigated. Several experiments involving crystal structure determination, IR spectroscopy, and ultra-high-resolution cryospray-ionization mass spectrometry were performed. The crystal structures of [CuCl₂(H₂O)]·0.5(CH₃)₂CO (1), [Cu₂(CH₃CN)₂Cl₄] (2), [Cu₃(CH₃CN)₃Cl₆] (3), [Cu₃Cl₆(THF)₄] (4), [Cu(DMSO)₂Cl₂] (5), (H₂N(CH₃)₂)₂[CuCl₃] (6), and [Cu₄OCl₆(THF)(urea)₃]·3THF·urea (8) are reported herein. It can be clearly demonstrated that μ₄-oxido copper clusters of the formula [Cu₄OCl₆(solvent)₄] are the main product from the reactions of CuCl₂·2H₂O and basic coreagents. As a final result of these experiments, it can be stated that μ₄-oxido copper clusters most likely play an important role in the mechanism of copper chloride-catalyzed reactions.