Carbon-Nitrogen Bond Cleavage by a Thorium-NHC-bpy Complex

Actinide complexes demonstrate unparalleled reactivity towards small molecules. However, utilizing these powerful transformations in a predictable and deliberate manner remains challenging. Therefore, developing actinide systems that not only perform noteworthy chemistry but also demonstrate controllable reactivity is a key goal. We describe a bis(NHC)borate thorium‐bpy complex (1) that is capable of reductively cleaving the R−NC bond in a series of organic isocyanides. In contrast to most actinide‐mediated bond activations, the dealkylation event mediated by 1 is remarkably general and yields very well‐defined products that assist in mechanistic elucidation. Synthesis of the rearranged but‐3‐enyl product from the reaction of 1 and cyclopropylmethyl isocyanide supports the notion of a radical‐based mechanism. Thors Hammer: Ein Bis(NHC)borat‐Thorium‐Bipyridin‐Komplex (1) spaltet reduktiv die R‐NC‐Bindung in einer Reihe organischer Isocyanide. Anders als für Actinoid‐vermittelte Bindungsaktivierungen üblich, liefert diese Desalkylierung wohldefinierte Produkte über ein außergewöhnlich breites Substratspektrum. Die Reaktion von 1 mit Cyclopropylmethylisocyanid unter Bildung des umgelagerten But‐3‐enyl‐Produkts spricht für einen radikalischen Mechanismus.