Abstract
The formation of ionic three-membered phosphorus heterocycles from unsaturated hydrocarbons and mono-adducts of the phosphenium ion has been investigated using ab initio molecular orbital calculations at the G2 level. In appropriate cases, these so-called exchange reactions are exothermic with no overall barrier, and they should therefore be experimentally feasible. Thus, we suggest that phosphenium ions with one lone-pair donor ligand may represent a valuable new reagent in the synthesis of ionic three-membered phosphorus heterocycles. In addition, we discuss the nature of the electronic interactions in the bis-adducts of the phosphenium ion with two lone-pair donors, two π donors, or with one lone-pair donor and one π donor. Keywords: G2 theory; Three-membered heterocyclic ions; Mono-adducts of the phosphenium ion; Exchange reactions
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