An Unexpected Pathway in the Cage Opening and Aggregation of P4

Graceful degradation: The reaction of the [(Me3Si)3Si]− ion with white phosphorus results in a new phosphorus‐based dianion (see scheme; R=Si(SiMe3)3), apparently arising from the unexpected aggregation of two [RP4]− units into a P7 nortricyclic core with an exo anionic P atom. The formation of this dianion sheds new light on the mechanism(s) of P4 degradation by nucleophiles and the ability of silyl substituents to direct product formation.