Dialumene‐Mediated Production of Phosphines through P4 Reduction

The formation of phosphorus‐rich alanes featuring butterfly‐like geometries is achieved. The two‐electron reduction products feature a unique P 4 2− structure and can act as a source of P 3− . The treatment of these phosphorus containing products with electrophiles under mild conditions results in the formation of different phosphines. This approach eliminates the need for high temperatures and/or high pressures, which are commonly required in industrial processes for the preparation of useful phosphines.The activation and further functionalization of white phosphorus (P 4 ) by main group complexes has become an increasingly studied topic in recent times. Herein, we report the controlled formation of phosphorus‐rich alanes featuring butterfly‐like geometries from the selective reaction of P 4 with dialumenes, ([L(I i Pr)Al] 2 ) ( 1 : L=Tripp=2,4,6‐ i Pr 3 C 6 H 2 ; 2 : L= t Bu 2 MeSi; I i Pr=[MeCN( i Pr)] 2 C)). The two‐electron‐reduction product of P 4 features a P 4 2− structure and is shown to be able to act as a source of P 3− . Treatments of different electrophiles (e.g., chlorotrimethylsilane (Me 3 SiCl), iodotrimethylsilane (Me 3 SiI), HCl, or acetyl chloride (CH 3 COCl)) with these alanes under mild conditions gave the corresponding phosphines (e.g., P(SiMe 3 ) 3 , PH 3 , or P(COCH 3 ) 3 ).