Abstract
The preparation of novel copper(I) complexes of diazabutadiene (DAB) ligands with aliphatic backbones is reported. [Cu(DABR)2](BF4), [Cu(DABR)(NCMe)2](BF4) and [CuCl(DABR)] are easily synthesised and air‐stable. These complexes, which remain scarce in the literature, have been fully characterised, and their behaviour both in the solid state as well as in solution has been studied by means of X‐ray crystallography, NMR and UV/Vis spectroscopy.
Highlights
Schiff bases are ubiquitous ligands for transition metals and they have played a major role in the development of their coordination chemistry, and of their catalytic,[1] and biochemical[2] uses
No mono-diimine copper(I) complexes could be accessed when a 1:1 Cu/DABR stoichiometry was used in different solvents (DCM, acetone or MeCN), and only the reported homoleptic complexes were isolated in all cases
A single resonance at 8.0 ppm was obtained at room temperature for this experiment. These results show that even if they might not be isolable, [Cu(DABR)(NCMe)2]BF4 complexes can be formed as diluted solutions either by dilution of pre-isolated [Cu(DABR)2]BF4 complexes or by the reaction of the ligand with a large excess (i.e. 5 equiv) of the copper source
Summary
Schiff bases are ubiquitous ligands for transition metals and they have played a major role in the development of their coordination chemistry, and of their catalytic,[1] and biochemical[2] uses. The rigidity of the phen ligands is considered to favour metal coordination by preventing rotation around the C‒C bond on the backbone This feature is relevant as many of these copper(I) complexes exhibit a low configurational stability in solution and their speciation is hard to control even in noncoordinating solvents.[6] Bis(N-arylimino)acenaphthene (BIAN) ligands have shown a similar behaviour, while having markedly different properties as the two exocyclic imine groups are not part of an heteroaromatic system.[7] The control and/or understanding of the coordination environment of metal centres is essential for the design and development of catalysts, materials or bioinorganic models. The structure of these complexes both in the solid state and in solution has been carefully examined
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