Hydrophosphination-type reactivity promoted by bismuth phosphanides: scope and limitations

Area of Science:

• Organometallic chemistry
• Bismuth chemistry
• Phosphorus chemistry

Background:

• Bismuth complexes with phosphanide ligands are valuable synthetic intermediates.
• Understanding the reactivity of terminal phosphanides is crucial for developing new catalytic processes.

Purpose of the Study:

• To investigate the reaction of phenyl isocyanate with a terminal bismuth phosphanide complex.
• To explore the liberation of hydrophosphination products from bismuth centers.
• To assess the potential for catalytic turnover in these systems.

Main Methods:

• Synthesis of the terminal bismuth phosphanide complex Bi(NONAr)(PCy2).
• Reaction of the bismuth complex with phenyl isocyanate.
• Liberation of the hydrophosphination product using diphenylphosphine (HPPh2).

Main Results:

• Phenyl isocyanate successfully inserts into the Bi-P bond, forming a κ2N,O-phosphanylcarboxamidate complex.
• The hydrophosphination product can be liberated from the bismuth center.
• The resulting diphenylphosphanide product is unstable and decomposes, inhibiting catalytic turnover.

Conclusions:

• The reaction demonstrates a new route to phosphanylcarboxamidate complexes via isocyanate insertion.
• Product instability of the diphenylphosphanide derivative prevents its use in catalytic applications.
• Further research is needed to stabilize such intermediates for potential catalytic cycles.