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

• Published in: Angewandte Chemie International Edition 2016-01, Vol.55 (2), p.613-617
• Main Authors: Borger, Jaap E., Ehlers, Andreas W., Lutz, Martin, Slootweg, J. Chris, Lammertsma, Koop
• Format: Article
• Language: English
• Subjects: Anions; boranes; Carbon; Cations; Lewis acid; Lewis acids; organophosphorus compounds; Phosphorus; Stabilization
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201508916

The transient bicyclo[1.1.0]tetraphosphabutane anion, generated from white phosphorus (P4) and Mes*Li (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 P4 derivative. 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 Mes*Li (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.