Masked P(III)/P(V) Frustrated Lewis Pair for C-H and X-H Bond Cleavage and Catalytic Hydroarylation of Alkenes

Abstract

Frustrated Lewis pairs (FLPs) have been realized for a wide range of element combinations, yet systems constructed from two phosphorus centers in distinct oxidation states remain unexplored. Here, we report an intramolecular dative R3P→PR₄⁺ bond that functions as a masked FLP. The architecture enables the heterolytic activation of C-H and X-H bonds (X = O, N), affording phosphonium/phosphorane products. The cooperative reactivity is further exploited in the hydroarylation of alkenes, demonstrating how P-P frameworks featuring mixed phosphorus oxidation states can be harnessed for main-group catalysis.