Metal‐Assisted, Reversible Phosphinyl Phosphination of the Carbon–Nitrogen Triple Bond in a Nitrile

Abstract

Split P's: Phosphinyl-substituted N-heterocyclic phosphines react by unprecedented metal-assisted addition of the PP bond to a nitrile triple bond to give complexes of hybrid bisphosphines. Surprisingly, the addition is reversible, and cleavage of the nitrile at high temperature permits controlled access to novel phosphenium–phosphide complexes (see scheme; only crucial parts of the structures are depicted).