Synthesis and Oligomerization of Cyclodiphosph(V)azene Adducts

The reaction of R1R2PCl (R1 = Me, Ph; R2 = Ph, oTol) with N,N′‐bis(trimethylsilyl)sulfur diimide in the presence of GaCl3 yields Lewis acid/base adducts of the corresponding cyclodiphosph(V)azenes: [MePhPN]2·(GaCl3)2, [Me(dmp)PN]2·(GaCl3)2 (dmp = 2,6‐dimethylphenyl), and [Ph(oTol)PN]2·(GaCl3)2. The same synthetic protocol was applied for the model compound Ph2AsCl. All isolated products were characterized spectroscopically and by single‐crystal X‐ray diffraction studies. Their ability to form oligomers/polymers induced by ion of the Lewis acid was investigated with the model compounds [MePhPN]2·(GaCl3)2 and [Ph2PN]2·(GaCl3)2. The synthesis and base‐induced oligomerization of adducts of cyclodiphosph(V)azenes were studied by 31P NMR spectroscopy, mass spectrometry, and single‐crystal X‐ray diffraction.