μ₃‐Imido‐Functionalized Chevrel–Sergent‐Type Molecular Clusters, a New Class of Inorganic–Organic Hybrid Compounds: Preparations and Alkylation Reactions

Under extremely mild conditions, [Re6Q5Cl9]− ions (Q  S, Se) react with bis(trimethylsilyl)amine derivatives to give clusters of the type [Re6Q5(μ3-NSiMe3)Cl8]2− (shown on the right). These are isostructural and isoelectronic with the Chevrel–Sergent cluster cores [Mo6Q8]4−. The μ3-imido-functionalized clusters react with electrophiles and thus offer opportunities to extend the chemistry of genuine inorganic–organic hybrid compounds.