51 / 2023-08-14 16:13:48

Cobalt-Mediated White Phosphorus Activation and Functionalization: PNP Ligands Case

P4 activation,P4 functionalization,polyphosphorus compounds,cobalt complexes

New Technologies in Phosphorus Chemistry > 4) Inorganic phosphorus chemistry

Transition-metal mediated white phosphorus activation and functionalization have attracted increasing attention as an ecological alternative to P₄ chlorination pathway to the important phosphorus products [1,2].

We report a facile approach for P₄ activation, transformation and subsequent functionalization using cobalt complexes bearing PNP ligands [3]. The use of N,N-bis(diphenylphosphino)amine as a ligand allows one to transform P₄ tetrahedron into a zig-zag chain with the formation of complex [Co(Ph₂PNHP(Ph₂)PPPPP(Ph₂)NHPPh₂)]BF₄ (1). The presence of organic substituent at nitrogen atom in PNP ligand enables one to obtain complexes 2-4 with η¹-coordinated P₄ molecule, which indicates the crucial role of N-H bond in transformation of white phosphorus tetrahedron and gives valuable hints to the mechanism of this reaction. Additionally, complex 1 can readily be functionalized by means of the reaction with Ph₂PCl leading to the formation of a new complex 5 bearing unique P₉-ligand. The obtained results provide opportunities for facile construction of new polyphosphorus ligands in the coordination sphere of transition metal complexes.





Fig. 1 Activation and functionalization of P₄ in the coordination sphere of cobalt complexes



Keywords：P₄ activation; P₄ functionalization; polyphosphorus compounds; cobalt complexes





Reference

[1] Giusti, L.; Landaeta, V.R.; Vanni, M.; Kelly, J.A.; Wolf, R.; Caporali, M. Coord. Chem. Rev. 2021, 441, 213927.

[2] Hoidn, C.M.; Scott, D.J.; Wolf, R. Chem. Eur. J. 2021, 27, 1886-1902.

[3] Kuchkaev, A.M.; Kuchkaev, A.M.; Khayarov, K.R.; Zueva, E.M.; Dobrynin, A.B.; Islamov, D.R.; Yakhvarov, D.G. Angew. Chem. Int. Ed., 2022, 61, e202210973; Angew. Chem. 2022, 134, e202210973.



This work was financially supported by the Russian Science Foundation (project no. 23-13-00427)