Xiong Yun, Dong Shicheng, Yao Shenglai, Dai Chenshu, Zhu Jun, Kemper Sebastian, Driess Matthias
Department of Chemistry: Metalorganic and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623, Berlin, Germany.
State Key Laboratory of Physical Chemistry of Solid Surface and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. China.
Angew Chem Int Ed Engl. 2022 Sep 12;61(37):e202209250. doi: 10.1002/anie.202209250. Epub 2022 Aug 8.
White phosphorus (P ) undergoes degradation to P moieties if exposed to the new N,N-bis(silylenyl)aniline PhNSi 1 (Si=Si[N(tBu)] 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 PhNSi P 2 into 3 and 4 could be uncovered. It became evident that 2 reacts readily with both reactants P and 1 to afford either the polycyclic Si=P-containing product [PhNSi P ] P 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 as well as the reaction conditions. Compounds 3 and 4 can be converted into each other by reactions with 1 and P , 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.
如果白磷（P₄）暴露于新型N，N-双（硅烯基）苯胺PhNSi₁（Si = Si[N(tBu)]₂CPh），它会降解为磷部分，生成首个可分离的2,5-二硅-3,4-二磷吡咯2以及两种新型官能化的Si = P双键化合物3和4。非芳香性的2,5-二硅-3,4-二磷吡咯PhNSi₂P₂转化为3和4的途径得以揭示。很明显，2能与反应物P₄和1都轻松反应，根据所采用的1和P₄的摩尔比以及反应条件，生成多环含Si = P的产物[PhNSi₂P₂]P₄ 3或前所未有的含共轭Si = P - Si = P - Si = NPh链的化合物4。化合物3和4可分别通过与1和P₄反应相互转化。所有新化合物1 - 4都通过单晶X射线衍射分析等方法得到了明确表征。此外，通过密度泛函理论（DFT）计算确定了2 - 4的电子结构。
