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Investigations Concerning [Cu 4 OX 6 L 4 ] Cluster Formation of Copper(II) Chloride with Amine Ligands Related to Benzylamine
Author(s) -
Becker Sabine,
Behrens Ulrich,
Schindler Siegfried
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201500115
Subject(s) - chemistry , copper , acetonitrile , cluster (spacecraft) , cyclohexylamine , amine gas treating , crystal structure , ligand (biochemistry) , chloride , crystallography , catalysis , isostructural , benzylamine , medicinal chemistry , stereochemistry , organic chemistry , biochemistry , receptor , computer science , programming language
The μ 4 ‐oxido motif is well known in copper clusters and often forms spontaneously and unexpectedly; however, little is known about the reaction conditions that generate μ 4 ‐oxido clusters. This is surprising because these μ 4 ‐oxido copper clusters seem to play an important role in catalysis. Herein, a systematic investigation of μ 4 ‐oxido cluster formation is reported. The influence of several factors on cluster formation was studied, namely, the ligand environment, the central chalcogenide atom, and the bridging halido ligands. In this context, the crystal structures of the copper clusters and complexes [Cu 4 OCl 6 L 2 4 ][Cu L 2 2 Cl 2 ] ( L 2 = phenethylamine), [Cu L 3 2 Cl 2 ] ( L 3 = N ‐methylbenzylamine), [Cu 4 OCl 6 L 4 4 ] ( L 4 = N , N ‐dimethylbenzylamine), [Cu L 5 4 Cl 2 ] ( L 5 = cyclohexylamine), and [Cu 4 OCl 6 L 6 4 ] · 1.5[Cu L 6 2 Cl 2 ] ( L 6 = cyclohexanemethylamine) as well as that of H L 4 Cl are reported. Furthermore, the acetonitrile complexes [Cu(CH 3 CN) 4 ][CuBr 4 ], [Cu(CH 3 CN)Br], and [Cu(CH 3 CN)Br 2 ] were obtained and characterized within attempts to prepare a μ 4 ‐sulfido unit. The reaction conditions that generate μ 4 ‐oxido cluster units are discussed in more detail.