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: <b>1-Ln</b> (<b>Ln</b> = Tb³⁺, Dy³⁺, Ho³⁺, Er³⁺, Tm³⁺, and Yb³⁺), <b>1-La</b>, and <b>1-Ti</b> (an early transition metal analogue). The one-electron oxidation of the tris(amido) ligand was conducted to generate semi-iminato complexes <b>2-Ln</b>, <b>2-La</b>, and <b>2-Ti</b>, and these complexes were studied using EPR. Tris(amido) complexes <b>1-Ln</b>, <b>1-La</b>, and <b>1-Ti</b> 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 <b>1-La</b>). Computational methods were employed to further elucidate the electronic structures of these complexes. Lastly, complexes <b>1-Ln</b>, <b>1-La</b>, and <b>1-Ti</b> 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.