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<i>N,N</i>‐Bis(Silylenyl)Aniline
Yun Xiong, Shicheng Dong, Shenglai Yao, Chenshu Dai, Jun Zhu, Sebastian Kemper, Matthias Drieß
Abstract
Abstract White phosphorus (P 4 ) undergoes degradation to P 2 moieties if exposed to the new N,N ‐bis(silylenyl)aniline PhN Si 2 1 ( Si =Si[N( t Bu)] 2 CPh), 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 PhN Si 2 P 2 2 into 3 and 4 could be uncovered. It became evident that 2 reacts readily with both reactants P 4 and 1 to afford either the polycyclic Si=P‐containing product [PhN Si 2 P 2 ] 2 P 2 3 or the unprecedented conjugated Si =P− Si =P− Si =NPh chain‐containing compound 4 , depending on the employed molar ratio of 1 and P 4 as well as the reaction conditions. Compounds 3 and 4 can be converted into each other by reactions with 1 and P 4 , 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.