Rapid Oxygen Atom Transfer at a Catalysis-Relevant Ni(I)–Alkyl Complex with N2O

To improve our understanding of Ni-catalyzed alcohol formation with N2O, a catalytically relevant Ni­(I)–alkyl was synthesized and characterized (EPR, NMR). The complex, prepared via comproportionation and transmetalation, reacted with N2O at ambient temperature within 1 min, producing alcohol and N2. This contrasts sharply with slower reactions of (bpy)­NiEt2 (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 N2O’s inertness, highlighting its potential as a versatile oxidant in synthesis.