Synthesis and Oligomerization of Cyclodiphosph(V)azene Adducts

Abstract The reaction of R 1 R 2 PCl (R 1 = Me, Ph; R 2 = Ph, o Tol) with N , N′ ‐bis(trimethylsilyl)sulfur diimide in the presence of GaCl 3 yields Lewis acid/base adducts of the corresponding cyclodiphosph(V)azenes: [MePhPN] 2 · (GaCl 3 ) 2 , [Me(dmp)PN] 2 · (GaCl 3 ) 2 (dmp = 2,6‐dimethylphenyl), and [Ph( o Tol)PN] 2 · (GaCl 3 ) 2 . The same synthetic protocol was applied for the model compound Ph 2 AsCl. All isolated products were characterized spectroscopically and by single‐crystal X‐ray diffraction studies. Their ability to form oligomers/polymers induced by abstraction of the Lewis acid was investigated with the model compounds [MePhPN] 2 · (GaCl 3 ) 2 and [Ph 2 PN] 2 · (GaCl 3 ) 2 .