VU - Publication Angewandte Chemie
Angewandte Chemie 2015, doi: 10.1002/anie.201508916: Stabilization and Transfer of the Transient [Mes*P4]− Butterfly Anion Using BPh3 - Jaap E. Borger, Dr. Andreas W. Ehlers, Dr. Martin Lutz, Dr. Chris Slootweg, Prof.dr. Koop Lammertsma
Functionalizing white phosphorus (P4) directly is imperative if chlorinated intermediates are to be avoided in producing organophosphorus compounds, but the high and unpredictable reactivity of the P4 tetrahedron makes it a challenge to develop such processes. In an exploratory study (Angew. Chem. Int. Ed. 2014, 53, 12836-12839), we showed that P4 reacts with sterically congested aryl lithium reagents and B(C6F5)3 to give LA-stabilized bicyclo[1.1.0]tetraphosphabutane anions. Now, we demonstrate that these fleeting intermediates are also trappable with the much milder Lewis acid BPh3, giving a novel stabilized anion which can be used as [RP4]− transfer agent, reacting cleanly with neutral Lewis acids (B(C6F5)3, BH3 and W(CO)5) to afford unique mono and doubly coordinated butterfly anions and with the trityl cation to form a neutral, non-symmetrical, all-carbon substituted P4 derivative. This reaction path enables a simple, stepwise functionalization of white phosphorus.