Rapid Oxygen Atom Transfer at a Catalysis-Relevant Ni(I)–Alkyl Complex with N<sub>2</sub>O
Ana Mateos-Calbet, Paolo Cleto Bruzzese, Markella Aliki Mermigki, Alexander Schnegg, Dimitrios A. Pantazis, Josep Cornellà
Abstract
High Resolution Image Download MS PowerPoint Slide 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.