Bonding and Reactivity in Terminal versus Bridging Arenide Complexes of Thorium Acting as ThII Synthons

Abstract

Thorium redox chemistry is extremely scarce due to the high stability of Th^IV . Here we report two unique examples of thorium arenide complexes prepared by reduction of a Th^IV -siloxide complex in presence of naphthalene, the mononuclear arenide complex [K(OSi(O^t Bu)₃ )₃ Th(η⁶ -C₁₀ H₈ )] (1) and the inverse-sandwich complex [K(OSi(O^t Bu)₃ )₃ Th]₂ (μ-η⁶ ,η⁶ -C₁₀ H₈ )] (2). The electrons stored in these complexes allow the reduction of a broad range of substrates (N₂ O, AdN₃ , CO₂ , HBBN). Higher reactivity was found for the complex 1 which reacts with the diazoolefin IDipp=CN₂ to yield the unexpected Th^IV amidoalkynyl complex 5 via a terminal N-heterocyclic vinylidene intermediate. This work showed that arenides can act as convenient redox-active ligands for implementing thorium-ligand cooperative multielectron transfer and that the reactivity can be tuned by the arenide binding mode.

Keywords: Actinides; Inverse-Sandwich Complexes; Redox Reactivity; Redox-Active Ligands; Thorium.