Design of non-ionic carbon superbases: second generation carbodiphosphoranes

A new generation of carbodiphosphoranes (CDPs), incorporating pyrrolidine, tetramethylguanidine, or tris(dimethylamino)phosphazene as substituents is introduced as the most powerful class of non-ionic carbon superbases on the basicity scale to date. The synthetic approach as well as NMR spectroscopic and structural characteristics in the free and protonated form are described. Investigation of basicity in solution and in the gas phase by experimental and theoretical means provides the to our knowledge first reported pK(BH)(+) values for CDPs in the literature and suggest them as upper tier superbases.