Facile C≡O Triple Bond Cleavage of Carbon Monoxide by a Mononuclear Uranium Borohydride Complex

ABSTRACT

Complete scission of the C≡O triple bond in carbon monoxide by an actinide complex has so far been restricted to multimetallic nitride‐bridged systems, where the reaction proceeds via formation of strong C─N multiple bonds. Here we report an alternative mode of complete CO cleavage mediated by a mononuclear uranium(IV) borohydride complex supported by a double layer N–P ligand at room temperature. Single‐crystal x‐ray diffraction reveals that the oxygen atom becomes bonded to both uranium and boron (U–O–B), while the carbon atom is inserted into a new hydrocarbyl framework, forming U─C, C─C, and C─Si bonds. Computational studies elucidate a cooperative mechanism involving CO insertion into the U–H–B linkage followed by low‐barrier rearrangements. This work demonstrates complete CO cleavage by a mononuclear actinide complex operating through a U–H–B cooperative pathway, thereby establishing an alternative, nitride‐free route for this transformation at a single uranium center.