A Bench-Stable Fluorophosphine Nickel(0) Complex and Its Catalytic Application.

Area of Science:

• Organometallic Chemistry
• Catalysis
• Inorganic Synthesis

Background:

• Nickel(0) complexes are crucial catalysts in organic synthesis but often suffer from instability.
• Fluorophosphine ligands are reactive and tend to disproportionate, limiting their use in stable complexes.
• Existing nickel(0) sources like [Ni(COD)2] present stability challenges.

Purpose of the Study:

• To synthesize and characterize a novel, stable nickel(0) complex featuring fluorophosphine ligands.
• To investigate the in situ formation mechanism of the nickel(0) complex.
• To evaluate the catalytic activity and versatility of the new complex in coupling reactions.

Main Methods:

• One-pot synthesis of [Ni(PFPh2)4] from [Ni(MeCN)4](BF4)2 and Ph2P(═O)-PPh2.
• Characterization of the resulting nickel(0) complex.
• Testing the catalytic performance of [Ni(PFPh2)4] in various coupling reactions using dppf as a co-ligand.

Main Results:

• Successful synthesis of a highly stable air- and water-tolerant nickel(0) complex, [Ni(PFPh2)4].
• The synthesis involves a unique in situ reduction of Ni(II) to Ni(0) and simultaneous fluorination.
• The [Ni(PFPh2)4] complex exhibited high catalytic activity and versatility in coupling reactions, outperforming [Ni(COD)2].

Conclusions:

• [Ni(PFPh2)4] represents a significant advancement as a stable and highly active nickel(0) pre-catalyst.
• The developed synthetic route offers a unique approach to generating stable nickel(0) complexes with challenging ligands.
• This new catalyst opens avenues for more robust and efficient catalytic processes in organic synthesis.