The cage compound [DippP5Cl][GaCl4] (Dipp=2,6-diisopropylphenyl) reacts with an NHC (N-heterocyclic carbene) by an unprecedented [3+2] fragmentation of the P5+ core. This yields an imidazoliumyl-substituted P3 species featuring a triphosphaallyl anion motif and a neutral P2 compound. The mechanism of the fragmentation reaction was elucidated by means of experimental and quantum chemical methods.
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