Reaction of P 4 with in situ Formed cyclo ‐Triphosphatriazenium Cation [(DmpNP) 3 Cl 2 ] + (Dmp = 2,6‐Dimethylphenyl)

The controlled activation of white phosphorus, P 4 , 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 P 4 in the presence of GaCl 3 as Lewis acid for the targeted synthesis of mono‐ and dicationic phosphorus‐rich cage compounds [(DmpNP) 2 (P 4 )Cl][GaCl 4 ] ( 8a [GaCl 4 ]) and [(DmpNP) 2 (P 4 ) 2 ][Ga 2 Cl 7 ] 2 ( 9a [Ga 2 Cl 7 ] 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 (P 4 )Cl] + ( 8b + ) and [(DippNP) 2 (P 4 ) 2 ] 2+ ( 9b 2+ ; 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 P 2 N 2 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 (P 4 )Cl 2 ] + ( 10a + ) and [(DmpNP) 3 (P 4 ) 2 Cl] 2+ ( 11a 2+ ) via cyclo ‐triphosphatriazenium cation [(DmpNP) 3 Cl 2 ] + ( 4a + ).