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Copper chloride catalysis is an important research area in organic as well as inorganic chemistry. However, so far only little is known in most cases about the detailed reaction mechanism. The molecular structures of copper agglomerates that are formed when CuCl2·2H2O is dissolved in coordinating solvents in the absence and presence of a basic coreagent such as NaOtBu (basic coreagents usually are applied in copper chloride catalysis) have been determined. The results of this work clearly document that multinuclear copper clusters most likely play an important role in copper chloride catalysis.
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 NaOtBu 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.
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