Metalate-Mediated Functionalization of P4 by Trapping Anionic [Cp*Fe(CO)2(η1-P4)]− with Lewis Acids

Abstract

The development of selective functionalization strategies ofwhite phosphorus (P4) is important to avoid the current chlori-nated intermediates. The use of transition metals (TMs) couldlead to catalytic procedures, but these are severely hamperedby the high reactivity and unpredictable nature of the tetrahe-dron. Herein, we report selective first steps by reacting P4witha metal anion [Cp*Fe(CO)2](Cp*= C5(CH3)5), which, in thepresence of bulky Lewis acids (LA; B(C6F5)3or BPh3), leads tounique TM-substituted LA-stabilized bicyclo[1.1.0]tetraphos-phabutanide anions [Cp*Fe(CO)2(h1-P4·LA)]. Their P-nucleo-philic site can be subsequently protonated to afford the transi-ent LA-free neutral butterflies exo,endo- and exo,exo-Cp*Fe-(CO)2(h1-P4H), allowing controllable stepwise metalate-mediat-ed functionalization of P4.