Kuchkaev Airat M, Kuchkaev Aidar M, Khayarov Khasan R, Zueva Ekaterina M, Dobrynin Alexey B, Islamov Daut R, Yakhvarov Dmitry G
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Street 8, Kazan, 420088, Russian Federation.
Alexander Butlerov Institute of Chemistry, Kazan Federal University, Kremlyovskaya Street 18, Kazan, 420008, Russian Federation.
Angew Chem Int Ed Engl. 2022 Nov 21;61(47):e202210973. doi: 10.1002/anie.202210973. Epub 2022 Oct 25.
Transition-metal mediated white phosphorus activation is of high interest as an ecological alternative to P chlorination pathway to the practically useful phosphorus products. Herein, we report a facile approach for P 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 tetrahedron into a zig-zag chain with the formation of complex [Co(Ph PNHP(Ph )PPPPP(Ph )NHPPh )]BF (4). The presence of organic substituent at nitrogen atom in PNP ligand enables one to obtain complexes with η -coordinated P molecule, which indicates a 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 PCl leading to the formation of a new complex bearing unique P -ligand. The obtained results provide opportunities for facile construction of new polyphosphorus ligands in the coordination sphere of transition metal complexes.
过渡金属介导的白磷活化作为一种生态友好的替代方法，用于从实用的磷产品的氯化磷途径中脱颖而出，备受关注。在此，我们报道了一种使用带有 PNP 配体的钴配合物进行磷活化、转化及后续功能化的简便方法。使用 N,N-双（二苯基膦基）胺作为配体能够将磷四面体转化为锯齿链，并形成配合物[Co(Ph PNHP(Ph )PPPPP(Ph )NHPPh )]BF (4)。PNP 配体中氮原子上有机取代基的存在使得能够获得与 η -配位磷分子的配合物，这表明 N-H 键在白磷四面体转化中起着关键作用。此外，配合物 4 可通过与 Ph PCl 反应轻松实现功能化，从而形成带有独特 P -配体的新配合物。所获得的结果为在过渡金属配合物的配位球中简便构建新的多磷配体提供了机会。
