The controlled reaction of P4 with in situ formed cyclo-triphosphatriazenium cation [(DmpNP)3Cl2]+ (Dmp = 2,6-dimethylphenyl) leads to the formation of mono- and dicationic derivatives [(DmpNP)3(P4)Cl2]+ and [(DmpNP)3(P4)2Cl]2+. The insertion reaction proceeds via a dicoordinate, cyclic phosphenium cation.
The 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+).