Pyridinylidenaminophosphines: Facile Access to Highly Electron‐Rich Phosphines

Electron‐rich tertiary phosphines are valuable species in chemical synthesis. However, their broad application as ligands in catalysis and reagents in stoichiometric reactions is often limited by their costly synthesis. Herein, we report the synthesis and properties of a series of phosphines with 1‐alkylpyridin‐4‐ylidenamino and 1‐alkylpyridin‐2‐ylidenamino substituents that are accessible in a very short and scalable route starting from commercially available aminopyridines and chlorophosphines. The determination of the Tolman electronic parameter (TEP) value reveals that the electron donor ability can be tuned by the substituent pattern at the aminopyridine backbone and it can exceed that of common alkylphosphines and N‐heterocyclic carbenes. The potential of the new phosphines as strong nucleophiles in phosphine‐mediated transformations is demonstrated by the formation of Lewis base adducts with CO(2) and CS(2). In addition, the coordination chemistry of the new phosphines towards Cu(I), Au(I), and Pd(II) metal centers has been explored, and a convenient procedure to introduce the most basic phosphine into metal complexes starting from air‐stable phosphonium salt is described.