Elucidating the Impact of Rare Earth or Transition Metal Identity on the Physical and Electronic Structural Properties of a Series of Redox-Active Tris(amido) Complexes

The use of redox-active ligands with the f-block elements has been employed to promote unique chemical transformations and explore their unique emergent electronic properties for a myriad of applications. In this study, we report eight new tris(amido) metal complexes: 1–Ln (Ln = Tb3+, Dy3+, Ho3+, Er3+, Tm3+, and Yb3+), 1–La, and 1–Ti (an early transition metal analogue). The one-electron oxidation of the tris(amido) ligand was conducted to generate semi-iminato complexes 2–Ln, 2–La, and 2–Ti, and these complexes were studied using EPR. Tris(amido) complexes 1–Ln, 1–La, and 1–Ti were fully characterized using a range of spectroscopic (NMR and UV–vis/NIR) and physical techniques (X–ray diffraction and cyclic voltammetry, with the exception of 1–La). Computational methods were employed to further elucidate the electronic structures of these complexes. Lastly, complexes 1–Ln, 1–La, and 1–Ti were probed as catalysts for alkyl–alkyl cross-coupling, and the initial rate of the reaction was measured to explore the influence of the metal ion.