LAUSR

Abstract The development of selective functionalization strategies of white phosphorus (P4) is important to avoid the current chlorinated intermediates. The use of transition metals (TMs) could lead to catalytic procedures, but these are severely hampered by the high reactivity and unpredictable nature of the tetrahedron. Herein, we report selective first steps by reacting P4 with a metal anion [Cp*Fe(CO)2]− (Cp*=C5(CH3)5), which, in the presence of bulky Lewis acids (LA; B(C6F5)3 or BPh3), leads to unique TM‐substituted LA‐stabilized bicyclo[1.1.0]tetraphosphabutanide anions [Cp*Fe(CO)2(η1‐P4⋅LA)]−. Their P‐nucleophilic site can be subsequently protonated to afford the transient LA‐free neutral butterflies exo,endo‐ and exo,exo‐Cp*Fe‐ (CO)2(η1‐P4H), allowing controllable stepwise metalate‐mediated functionalization of P4.