Homo‐ and Heteroleptic Copper(I) Complexes with Diazabutadiene Ligands: Synthesis, Solution‐ and Solid‐State Structural Studies

Copper-mediated reduction of azides under seemingly oxidising conditions: catalytic and computational studies

“…We started our optimisation studies with the screening of the [Cu(DAB)] complexes (DAB = diazabutadiene) we recently reported. 20 4-Nitrophenyl azide and [CuIJDAB Cy ) 2 ]BF 4 were chosen to test the effect of solvents in a model reaction (Table 1). All reactions were carried out in technical solvents and in the presence of air.…”

“…The percentage buried volume (%V B ) 28 for ImPy Ad and ImPy Dipp was found to be 39.0 and 41.2% compared to 43.6% for DAB Ad and 44.5% for DAB Dipp . 20 Next, the newly synthesised complexes were tested in the model reaction (Table 3). Overall, the tailored [CuIJDAB R )] complexes provided improved conversions into aniline with the exception of 2, which might be attributed to the instability of this copper complex.…”

“…Starting from [CuIJDAB Me ) 2 ] + I.1, one of the DAB Me ligands is displaced by water and aniline to form a tetracoordinated copper intermediate I.3. Considering the low configurational stability in solution of these complexes, 20 such displacement is expected to be straightforward when diluted. DAB DMA partially hydrolysed under catalytic conditions (hot toluene/water mixture) forming traces of 4-(dimethylamino)aniline, which would be enough for the first catalyst turnover to take place.…”

Electronic and Geometric Structures of Paramagnetic Diazadiene Complexes of Lithium and Sodium

“…1,4‐Diaza‐1,3‐dienes (DADs) are well established as highly versatile ligands for nearly every element in the periodic table . The list of stable DAD complexes encompasses main‐group metals, early and late transition metals, as well as the lanthanides and actinides . Important practical applications of metal diazadiene complexes include homogeneous catalysis, C−H bond activation, materials science, and the synthesis of single‐molecule magnets .…”

“…This electronic flexibility in addition to the possibility of tuning the steric properties of DADs by using various substituents at both the C and N atoms account for the high versatility of DAD ligands in coordination chemistry. Scheme shows the different coordination modes of DAD ligands that have been reported in the literature …”