The field of uncharged phosphorus superbases was expanded to include several new mono- and bisphosphazenyl phosphines. These novel bases have been systematically analyzed according to their basicity, nucleophilicity, chemical stability, donor capabilities and coordination behavior. They complement the missing link between extremely basic trisphosphazenyl phosphines and traditional tertiary phosphines by combining the stability and steric properties of tertiary phosphines like PtBu3 with the extreme donor capabilities of phosphazenyl phosphines. The aforementioned parameters that were established during this work allow the easy classification of newly synthesized bases. Several applications of these bases were presented, as ligands in transition metal catalysis as well as organocatalysts in a variety of transformations.
