Rapid Oxygen Atom Transfer at a Catalysis-Relevant Ni(I)-Alkyl Complex with NO.

To improve our understanding of Ni-catalyzed alcohol formation with NO, a catalytically relevant Ni(I)-alkyl was synthesized and characterized (EPR, NMR). The complex, prepared via comproportionation and transmetalation, reacted with NO at ambient temperature within 1 min, producing alcohol and N. This contrasts sharply with slower reactions of (bpy)NiEt (12 h) and catalytic systems (22 h). Theoretical studies suggest a stepwise organometallic Baeyer-Villiger mechanism via a Ni(II)-oxyl intermediate. The high reactivity of Ni(I)-alkyl challenges the notion of NO's inertness, highlighting its potential as a versatile oxidant in synthesis.