Dinuclear Copper(I) Complexes with Hexaaza Macrocyclic Dinucleating Ligands: Structure and Dynamic Properties

The synthesis and structural and spectroscopic characterization of a family of copper(I) complexes, containing a
dinucleating hexaaza macrocyclic ligand, of general formula [Cu2(L)(X)2]2+ (L = Me2p, Me2m, Me3p, or Me3m; X
= MeCN, n-PrCN, CO, t-BuNC, or PPh3) is described. This family of complexes contains ligands that differ from
one another in the number of methylenic units linking the tertiary amines and in the meta or para substitution of
their aromatic rings. The structural characterization in the solid-state includes a single-crystal X-ray diffraction analysis
of [Cu2(Me2p)(CO)2]2+ and of [Cu2(Me2m)(t-BuNC)2]2+. In solution, those complexes are structurally characterized
through NMR spectroscopy that also allows us to put forward and establish their fluxional behavior. Theoretical
calculations at the DFT level have also been performed in order to further analyze the relative energy of the
different potential isomers as well as to gain insight into their chemical properties. Finally, the influence of the
hexaaza ligands over different structural aspects as well as on its potential chemical reactivity is discussed.