An Isolable 2,5‐Disila‐3,4‐Diphosphapyrrole and a Conjugated Si=P−Si=P−Si=N Chain Through Degradation of White Phosphorus with a N,N‐Bis(Silylenyl)Aniline

White phosphorus (P4) undergoes degradation to P2 moieties if exposed to the new N,N‐bis(silylenyl)aniline PhNSi2 1 (Si=Si[N(tBu)]2CPh), furnishing the first isolable 2,5‐disila‐3,4‐diphosphapyrrole 2 and the two novel functionalized Si=P doubly bonded compounds 3 and 4. The pathways for the transformation of the non‐aromatic 2,5‐disila‐3,4‐diphosphapyrrole PhNSi2P2 2 into 3 and 4 could be uncovered. It became evident that 2 reacts readily with both reactants P4 and 1 to afford either the polycyclic Si=P‐containing product [PhNSi2P2]2P2 3 or the unprecedented conjugated Si=P−Si=P−Si=NPh chain‐containing compound 4, depending on the employed molar ratio of 1 and P4 as well as the reaction conditions. Compounds 3 and 4 can be converted into each other by reactions with 1 and P4, respectively. All new compounds 1–4 were unequivocally characterized including by single‐crystal X‐ray diffraction analysis. In addition, the electronic structures of 2–4 were established by Density Functional Theory (DFT) calculations. A novel geminal N,N‐bis(silylenyl)aniline 1 degrades white phosphorus (P4) furnishing the first isolable 2,5‐disila‐3,4‐ diphosphapyrrole 2. The latter further reacts readily with P4 and 1 to afford the polycyclic Si=P‐containing species 3 or the unprecedented conjugated Si=P−Si=P−Si=NPh chain‐containing compound 4 depending on the molar ratio of the reactants. Moreover, the products 3 and 4 can be converted into each other when treated with 1 and P4, respectively.