Molybdenum sulphide clusters as redox-active supports for low-valent uranium

Abstract

The preparation of an actinide substituted cubane cluster, (Cp*₃Mo₃S₄)Cp*UI₂, and its reduced derivatives are reported. Structural and spectroscopic investigations provide insight into the unique interactions between the actinide and its redox-active molybdenum sulphide metalloligand, serving as a model to study atomically-dispersed, low-valent actinide ions on MoS₂ surfaces. To probe the ability of the assembly to facilitate multielectron small molecule activation, the reactivity of the fully-reduced cluster, (Cp*₃Mo₃S₄)Cp*U, with azobenzene was investigated. Addition of the substrate results in the formation of a cis-bis-imido cluster, (Cp*₃Mo₃S₄)Cp*U(NPh)₂. Cooperative reactivity between the actinide and redox-active support facilitates the 4e⁻-reduction of substrate.