PNP Ligands in Cobalt‐Mediated Activation and Functionalization of White Phosphorus

Transition-metal mediated white phosphorus activation is of high interest as an ecological alternative to P 4  chlorination pathway to the practically useful phosphorus products. Herein, we report a facile approach for P 4  activation, transformation and subsequent functionalization using cobalt complexes bearing PNP ligands. The use of N,N -bis(diphenylphosphino)amine as a ligand allows one to transform P 4  tetrahedron into a zig-zag chain with the formation of complex [Co(Ph 2 PNHP(Ph 2 ) PPPP P(Ph 2 )NHPPh 2 )]BF 4 ( 4 ). The presence of organic substituent at nitrogen atom in PNP ligand enables one to obtain complexes with η 1 -coordinated P 4 molecule, which indicates the crucial role of N-H bond in transformation of white phosphorus tetrahedron. Additionally, complex 4  can readily be functionalized by means of the reaction with Ph 2 PCl leading to the formation of a new complex bearing unique P 9 -ligand. The obtained results provide opportunities for facile construction of new polyphosphorus ligands in the coordination sphere of transition metal complexes.