Rapid Oxygen Atom Transfer at a Catalysis-Relevant Ni(I)-Alkyl Complex with N(2)O

To improve our understanding of Ni-catalyzed alcohol formation with N(2)O, a catalytically relevant Ni(I)-alkyl was synthesized and characterized (EPR, NMR). The complex, prepared via comproportionation and transmetalation, reacted with N(2)O at ambient temperature within 1 min, producing alcohol and N(2). This contrasts sharply with slower reactions of (bpy)NiEt(2) (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 N(2)O's inertness, highlighting its potential as a versatile oxidant in synthesis.