Introduction of plumbole to f-element chemistry

Abstract

Herein, we present the synthesis and characterization of heteroleptic lanthanide complexes bearing a dianionic η⁵-plumbole ligand in their coordination sphere. The reaction proceeds via a salt elimination reaction between the dilithioplumbole ([Li(thf)]₂[1,4-bis-tert-butyl-dimethylsilyl-2,3-bis-phenyl-plumbolyl] = [Li₂(thf)₂(η⁵-L^Pb)]) and specifically designed [Ln(η⁸-COT^TIPS)BH₄] precursors (Ln = lanthanide, La, Ce, Sm, Er; COT^TIPS = 1,4-bis-triisopropylsilyl-cyclooctatetraenyl), that are capable of stabilizing a planar plumbole moiety in the coordination sphere of different trivalent lanthanide ions. In-depth ab initio calculations show that the aromaticity of the dianionic plumbole is retained upon coordination. Electron delocalization occurs from the plumbole HOMO to an orbital of mainly d-character at the lanthanide ion. The magnetic properties of the erbium congener were investigated in detail, leading to the observation of magnetic hysteresis up to 5 K (200 Oe s⁻¹), an unequivocal proof for single molecule magnet behavior in this system. The magnetic behavior of the erbium species can be modulated by manipulating the position of the lithium cation in the complex, which directly influences the bonding metrics in the central [(η⁵-L^Pb)Er(η⁸-COT^TIPS)]⁻ fragment. This allowed us to assess a fundamental magneto-structural correlation in an otherwise identical inner coordination sphere.