Journal article

Authors list: Becker, S; Dürr, M; Miska, A; Becker, J; Gawlig, C; Behrens, U; Ivanović-Burmazović, I; Schindler, S

Publication year: 2016

Pages: 3759-3766

Journal: Inorganic Chemistry

Volume number: 55

Issue number: 8

ISSN: 0020-1669

DOI Link: https://doi.org/10.1021/acs.inorgchem.5b02576

Publisher: American Chemical Society

Abstract: 

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(t)Bu 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.

Harvard Citation style: Becker, S., Dürr, M., Miska, A., Becker, J., Gawlig, C., Behrens, U., et al. (2016) Copper Chloride Catalysis: Do μ4-Oxido Copper Clusters Play a Significant Role?, Inorganic Chemistry, 55(8), pp. 3759-3766. https://doi.org/10.1021/acs.inorgchem.5b02576

APA Citation style: Becker, S., Dürr, M., Miska, A., Becker, J., Gawlig, C., Behrens, U., Ivanović-Burmazović, I., & Schindler, S. (2016). Copper Chloride Catalysis: Do μ4-Oxido Copper Clusters Play a Significant Role?. Inorganic Chemistry. 55(8), 3759-3766. https://doi.org/10.1021/acs.inorgchem.5b02576