Rapid Oxygen Atom Transfer at a Catalysis-Relevant Ni(I)–Alkyl Complex with N<sub>2</sub>O
To improve our understanding of Ni-catalyzed alcohol formation with N<sub>2</sub>O, a catalytically relevant Ni(I)-alkyl was synthesized and characterized (EPR, NMR). The complex, prepared via comproportionation and transmetalation, reacted with N<sub>2</sub>O at ambient temperature within 1 min, producing alcohol and N<sub>2</sub>. This contrasts sharply with slower reactions of (bpy)NiEt<sub>2</sub> (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<sub>2</sub>O's inertness, highlighting its potential as a versatile oxidant in synthesis.
Authors
- Dimitrios A. Pantazis (ORCID: https://orcid.org/0000-0002-2146-9065)
- Paolo Cleto Bruzzese (ORCID: https://orcid.org/0000-0002-2070-836X)
- Ana Mateos-Calbet (ORCID: https://orcid.org/0000-0003-4165-6009)
- Markella Aliki Mermigki (ORCID: https://orcid.org/0000-0002-6805-2945)
- Josep Cornellà (ORCID: https://orcid.org/0000-0003-4152-7098)
- Alexander Schnegg (ORCID: https://orcid.org/0000-0002-2362-0638)
Institutions
- Max-Planck-Institut für Kohlenforschung (DE)
- Max Planck Institute for Chemical Energy Conversion (DE)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2025-05-30
- DOI
- https://doi.org/10.1021/jacs.5c03351
- Citations
- 3
- Primary Topic
- Metal-Catalyzed Oxygenation Mechanisms
- Type
- article
- Field-Weighted Citation Impact
- 1.61
Funders
- Deutsche Forschungsgemeinschaft
- Bodossaki Foundation
- Max-Planck-Gesellschaft
- Studienstiftung des Deutschen Volkes