Rare-earth metal complexes with redox-active formazanate ligands

Abstract

The synthesis and characterisation of rare-earth metal complexes with redox-active formazanate ligands are described. Deprotonation of the neutral formazan ligand L¹H (L¹ = PhNNC(Ph)NNPh) with [Ln{N(SiMe₃)₂}₃] (Ln = Y, Sm, Dy) resulted in homoleptic tris(formazanate) complexes with the general formula [(L¹)₃Ln] (Ln = Y (1), Sm (2), Dy (3)), in which the central metal atom is coordinated by six N atoms, revealing a propeller-type structure. To generate heteroleptic complexes, a novel formazan ligand L²H (L² = {PhNNC(4-tBuPh)NNPh}) was employed. Salt metathesis by using the trivalent precursors [SmCp*₂(μ-Cl)₂K(thf)] (Cp* = η⁵-C₅Me₅) or [LnCp₂Cl]₂ (Cp = η⁵-C₅H₅, Ln = Dy, Yb) and [L²K(thf)] formed mono(formazanate) complexes, [L²SmCp*₂] (4) and [L²LnCp₂] (Ln = Dy (5), Yb (6)), respectively. Unexpectedly, a redox reaction occurred between [L²K(thf)] and the divalent ytterbium precursor, [YbI₂(thf)₂], generating the trivalent ytterbium complex [(L²)₃Yb] (7). When the neutral formazan ligand (L²H) reacted with [SmCp*₂(thf)₂], the oxidised samarium complex 4 was formed. These novel compounds were fully characterised and their electrochemical properties were explored by cyclic voltammetry.