Reactions of the lithium or sodium salt, [HC(CMeNDipp) 2 ]M (Dipp=2,6-diisopropylbenzene, M=Li or Na), with PBr 3 or PCl 3 affords a series of phosphenium cations that were characterized in the solid state by X-ray crystallography. Solid-state analysis reveals that for compounds 1 and 2, C–H activation of the ligand occurs and the phosphorus is bound to a nitrogen and carbon atom of the ligand. Compound 3 exhibits the more traditional nitrogen chelation of the ligand to the phosphorus atom.