Formation of a Decanuclear Organometallic Dysprosium Complex via a Radical-Radical Cross-Coupling Reaction.

Over the years, polynuclear cyclic or torus complexes have attracted increasing interest due to their unique metal topologies and properties. However, the isolation of polynuclear cyclic organometallic complexes is extremely challenging due to their inherent reactivity, which stems from the labile and reactive metal-carbon bonds. In this study, the pyrazine ligand undergoes a radical-radical cross-coupling reaction leading to the formation of a decanuclear [(Cp*) ₂₀ Dy ₁₀ (L1) ₁₀ ] ⋅ 12(C ₇ H ₈ ) (1; where L1 = anion of 2-prop-2-enyl-2H-pyrazine; Cp* = pentamethylcyclopentadienyl) complex, where all Dy ^III metal centres are bridged by the anionic L1 ligand. Amongst the family of polynuclear Ln organometallic complexes bearing Cp ^R ₂ Ln _x units (Cp ^R = substituted cyclopentadienyl), 1 features the highest nuclearity obtained to date. In-depth computational studies were conducted to elucidate the proposed reaction mechanism and formation of L1, while probing of the magnetic properties of 1, revealed slow magnetic relaxation upon application of a static dc field.
(© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)