[3+2] Fragmentation of an [RP5Cl]+ Cage Cation Induced by an N-Heterocyclic Carbene


  • This work was supported by the Fonds der Chemischen Industrie (FCI, Liebig scholarship for M.H.H.) and the German Science Foundation (DFG, WE 4621/2-1).


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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.