The Mechanochemistry of Carboranes

Abstract

Abstract We developed o ‐carborane as a new mechanophore by showing that the o ‐carborane cluster is the preferred scission site in chain‐centered polymers through ultrasonication mechanochemistry. Mechanistic studies are consistent with a predominately homolytic mechanism of chain scission. The mechanically generated monocarbaborane fragments are highly reactive toward alcohol nucleophiles. By contrast, carborane with a different regiochemistry ( m ‐carborane) maintained its high mechanical stability. DFT simulations provide insights into the origins of carborane's mechanical lability. This fundamental research provides a new stimulus for carborane cage activation.