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Herein, we report a facile approach for P<jats:sub>4<\/jats:sub> activation, transformation and subsequent functionalization using cobalt complexes bearing PNP ligands. The use of <jats:italic>N<\/jats:italic>,<jats:italic>N<\/jats:italic>\u2010bis(diphenylphosphino)amine as a ligand allows one to transform P<jats:sub>4<\/jats:sub> tetrahedron into a <jats:italic>zig\u2010zag<\/jats:italic> chain with the formation of complex [Co(Ph<jats:sub>2<\/jats:sub>PNHP(Ph<jats:sub>2<\/jats:sub>)<jats:italic>PPPP<\/jats:italic>P(Ph<jats:sub>2<\/jats:sub>)NHPPh<jats:sub>2<\/jats:sub>)]BF<jats:sub>4<\/jats:sub> (<jats:bold>4<\/jats:bold>). The presence of organic substituent at nitrogen atom in PNP ligand enables one to obtain complexes with \u03b7<jats:sup>1<\/jats:sup>\u2010coordinated P<jats:sub>4<\/jats:sub> molecule, which indicates a crucial role of N\u2212H bond in transformation of white phosphorus tetrahedron. Additionally, complex <jats:bold>4<\/jats:bold> can readily be functionalized by means of the reaction with Ph<jats:sub>2<\/jats:sub>PCl leading to the formation of a new complex bearing unique P<jats:sub>9<\/jats:sub>\u2010ligand. The obtained results provide opportunities for facile construction of new polyphosphorus ligands in the coordination sphere of transition metal complexes.<\/jats:p>","DOI":"10.1002\/anie.202210973","type":"journal-article","created":{"date-parts":[[2022,10,6]],"date-time":"2022-10-06T10:29:49Z","timestamp":1665052189000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":13,"title":["PNP Ligands in Cobalt\u2010Mediated Activation and Functionalization of White Phosphorus"],"prefix":"10.1002","volume":"61","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-2284-0081","authenticated-orcid":false,"given":"Airat M.","family":"Kuchkaev","sequence":"first","affiliation":[{"name":"Arbuzov Institute of Organic and Physical Chemistry FRC Kazan Scientific Center of RAS  Arbuzov Street 8 Kazan 420088 Russian Federation"},{"name":"Alexander Butlerov Institute of Chemistry Kazan Federal University  Kremlyovskaya Street 18 Kazan 420008 Russian 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