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

Journal article


Publication Details

Author(s): Becker S, Dürr M, Msika A, Becker J, Gawlig C, Behrens U, Ivanovic-Burmazovic I, Schindler S
Journal: Inorganic Chemistry
Publication year: 2016
Volume: 55
Journal issue: 8
Pages range: 3759-66
ISSN: 1520-510X


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.



FAU Authors / FAU Editors

Dürr, Maximilian
Lehrstuhl für Bioanorganische Chemie
Ivanovic-Burmazovic, Ivana Prof. Dr.
Lehrstuhl für Bioanorganische Chemie


How to cite

APA:
Becker, S., Dürr, M., Msika, A., Becker, J., Gawlig, C., Behrens, U.,... Schindler, S. (2016). Copper Chloride Catalysis: Do μ4-Oxido Copper Clusters Play a Significant Role? Inorganic Chemistry, 55(8), 3759-66. https://dx.doi.org/10.1021/acs.inorgchem.5b02576

MLA:
Becker, Sabine, et al. "Copper Chloride Catalysis: Do μ4-Oxido Copper Clusters Play a Significant Role?" Inorganic Chemistry 55.8 (2016): 3759-66.

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Last updated on 2018-22-09 at 12:10