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

Area of Science:

• Organometallic Chemistry
• Catalysis
• Synthetic Chemistry

Background:

• Understanding nickel-catalyzed reactions with nitrous oxide (N₂O) is crucial for synthetic applications.
• Previous methods involving N₂O as an oxidant were often slow and inefficient.

Purpose of the Study:

• To synthesize and characterize a catalytically relevant Ni(I)-alkyl complex.
• To investigate the reactivity of this complex with N₂O for alcohol formation.
• To elucidate the reaction mechanism.

Main Methods:

• Synthesis of Ni(I)-alkyl complex via comproportionation and transmetalation.
• Characterization using Electron Paramagnetic Resonance (EPR) and Nuclear Magnetic Resonance (NMR) spectroscopy.
• Reactivity studies with N₂O and theoretical calculations.

Main Results:

• The synthesized Ni(I)-alkyl complex reacted with N₂O at ambient temperature within 1 minute, producing alcohol and nitrogen gas (N₂).
• This reaction was significantly faster than previously reported methods using related nickel complexes or catalytic systems.
• Theoretical studies proposed a stepwise organometallic Baeyer-Villiger mechanism involving a Ni(II)-oxyl intermediate.

Conclusions:

• The high reactivity of the Ni(I)-alkyl complex challenges the perceived inertness of N₂O.
• This study highlights the potential of N₂O as a versatile oxidant in synthetic chemistry.
• The findings pave the way for developing new catalytic systems utilizing N₂O.