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.