Reaction of P4 with in situ Formed cyclo‐Triphosphatriazenium Cation [(DmpNP)3Cl2]+ (Dmp = 2,6‐Dimethylphenyl)

Abstract

AbstractThe controlled activation of white phosphorus, P4, provides a key entry point into many aspects of polyphosphorus chemistry. Herein, the reaction of cyclo‐diphosphadiazane derivative (DmpNPCl)2 (3a; Dmp = 2,6‐dimethylphenyl) and P4 in the presence of GaCl3 as Lewis acid for the targeted synthesis of mono‐ and dicationic phosphorus‐rich cage compounds [(DmpNP)2(P4)Cl][GaCl4] (8a[GaCl4]) and [(DmpNP)2(P4)2][Ga2Cl7]2 (9a[Ga2Cl7]2) is reported. Depending on the reaction conditions, formation of these types of cages, which are similar to those of the known cations [(DippNP)2(P4)Cl]+ (8b+) and [(DippNP)2(P4)2]2+ (9b2+; Dipp = 2,6‐diisopropylphenyl) is observed. However, due to the reduced steric requirements of the Dmp compared to the Dipp group, an interconversion process of the P2N2 framework of cyclo‐dichlorodiphosphadiazane 3a with the cyclo‐trichlorotriphosphatriazane 5a is observed, which leads also to the formation of mono‐ and dicationic derivatives [(DmpNP)3(P4)Cl2]+ (10a+) and [(DmpNP)3(P4)2Cl]2+ (11a2+) via cyclo‐triphosphatriazenium cation [(DmpNP)3Cl2]+ (4a+).