Molybdenum sulphide clusters as redox-active supports for low-valent uranium
Kamaless Patra1, William W Brennessel1, Ellen M Matson1
1Department of Chemistry, University of Rochester, Rochester, NY 14627, USA. matson@chem.rochester.edu.
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.
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