Stabilization and Transfer of the Transient [MesP4]- Butterfly Anion Using BPh3

Article abstract of DOI:10.1002/anie.201508916

The transient bicyclo[1.1.0]tetraphosphabutane anion, generated from white phosphorus (P₄) and MesLi (Mes=2,4,6-tBu₃C₆H₂), can be trapped by BPh₃ in THF. This Lewis acid stabilized anion can be used as an [RP₄]^- transfer agent, reacting cleanly with neutral Lewis acids (B(C₆F₅)₃, BH₃, and W(CO)₅) to afford unique singly and doubly coordinated butterfly anions, and with the trityl cation to form a neutral, nonsymmetrical, all-carbon-substituted P₄derivative. This reaction path enables a simple, stepwise functionalization of white phosphorus. Trap and transfer: The bicyclo[1.1.0]tetraphosphabutane anion (see scheme, center), generated from P₄ and MesLi (Mes=2,4,6-tBu₃C₆H₂), can be trapped by BPh₃ in THF. The anion can be used as an [RP₄]^- transfer agent, reacting with neutral Lewis acids (B(C₆F₅)₃, BH₃, and W(CO)₅) to afford unique singly and doubly coordinated butterfly anions and with the trityl cation to form a neutral, nonsymmetrical P₄ derivative.