title: Copper Chloride Catalysis: Do μ4-Oxido Copper Clusters Play a Significant Role?
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.
authors.affiliation: Institut für Anorganische und Analytische Chemie, Justus-Liebig-Universität Giessen , Heinrich-Buff-Ring 17, 35392 Giessen, Germany.
authors.forename: Sabine
authors.initials: S
authors.lastname: Becker
authors.affiliation: Lehrstuhl für Bioanorganische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg , Egerlandstrasse 1, 91058 Erlangen, Germany.
authors.forename: Maximilian
authors.initials: M
authors.lastname: Dürr
authors.affiliation: Institut für Anorganische und Analytische Chemie, Justus-Liebig-Universität Giessen , Heinrich-Buff-Ring 17, 35392 Giessen, Germany.
authors.forename: Andreas
authors.initials: A
authors.lastname: Miska
authors.affiliation: Institut für Anorganische und Analytische Chemie, Justus-Liebig-Universität Giessen , Heinrich-Buff-Ring 17, 35392 Giessen, Germany.
authors.forename: Jonathan
authors.initials: J
authors.lastname: Becker
authors.affiliation: Institut für Anorganische und Analytische Chemie, Justus-Liebig-Universität Giessen , Heinrich-Buff-Ring 17, 35392 Giessen, Germany.
authors.forename: Christopher
authors.initials: C
authors.lastname: Gawlig
authors.affiliation: Institut für Anorganische und Angewandte Chemie, Universität Hamburg , Martin-Luther-King-Platz 6, 20146 Hamburg, Germany.
authors.forename: Ulrich
authors.initials: U
authors.lastname: Behrens
authors.affiliation: Lehrstuhl für Bioanorganische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg , Egerlandstrasse 1, 91058 Erlangen, Germany.
authors.forename: Ivana
authors.initials: I
authors.lastname: Ivanović-Burmazović
authors.affiliation: Institut für Anorganische und Analytische Chemie, Justus-Liebig-Universität Giessen , Heinrich-Buff-Ring 17, 35392 Giessen, Germany.
authors.forename: Siegfried
authors.initials: S
authors.lastname: Schindler