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Benkö, Zoltan
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article
Spontaneous phosphorus-halogen bond cleavage in N-heterocyclic halogenophosphanes revisited
Abstract
P-bromo- and P-lodo-substituted N-heterocyclic phosphanes (NHP) were synthesized by halogen exchange starting from the P-chloro compound and characterized by spectroscopic data and X-ray diffraction studies. Whereas the Br-NHP still forms a molecular crystal, the solid-state structure of the I-derivative consists of ion-pairs which assemble via secondary P center dot center dot center dot 1 interactions to form one-dimensional coordination polymers. Computational Studies indicate that the bond dissociation is due to a combination of intramolecular stabilisation (aromatisation of the phosphenium cation formed) and intermolecular Lewis-acid/base interactions. Reaction of the I-NHP with I-2 proceeded under complete P-I bond cleavage to give an ionic phosphenium triiodide whose single-crystal X-ray diffraction Study revealed a unique supramolecular structure.