Metal-Free Bond Activation by Carboranyl Diphosphines

We report metal-free bond activation by the carboranyl diphosphine 1-P^tBu₂-2-PⁱPr₂-C₂B₁₀H₁₀. This main group element system contains basic binding sites and possesses the ability to cycle through two-electron redox states. The reported reactions with selected main group hydrides and alcohols occur via the formal oxidation of the phosphine groups and concomitant reduction of the boron cage. These transformations, which are driven by the cooperation between the electron-donating exohedral substituents and the electron-accepting cluster, differ from those of "regular" phosphines and are reminiscent of oxidative addition to transition metal centers, thus representing a new approach to metal-free bond activation.