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

2025/05/30 by Ana Mateos-Calbet, Paolo Cleto Bruzzese, Markella Aliki Mermigki +3 · 1 voice
Chemistry · Energy · #CO2 Reduction Techniques and Catalysts #Electrocatalysts for Energy Conversion #Metal-Catalyzed Oxygenation Mechanisms

paper · pdf · doi:10.1021/jacs.5c03351

openalex publication_date 2025/05/30 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/01

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.

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