Xiong Yun, Dong Shicheng, Yao Shenglai, Zhu Jun, Driess Matthias
Department of Chemistry: Metalorganics 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), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. China.
Angew Chem Int Ed Engl. 2022 Jul 11;61(28):e202205358. doi: 10.1002/anie.202205358. Epub 2022 May 19.
New types of metal-free white phosphorus (P ) activation are reported. While the phosphine-silylene-substituted dicarborane 1, CB-SiP (CB=ortho-C,C'-C B H , Si=PhC(tBuN) Si, P=P[N(tBu)CH ] ), activates white phosphorus in a 2 : 1 molar ratio to yield the P -chain containing species 2, the analogous bis(silylene)-substituted compound 3, CB-Si reacts with P in the molar ratio of 2 : 1 to furnish the first isolable 1,3-diphospha-2,4-disilabutadiene (Si=P-Si=P-containing) compound 4. For the latter reaction, two intermediates having a CB-Si P and CB-Si P core could be observed by multinuclear NMR spectroscopy. The compounds 2 and 4 were characterized including single-crystal X-ray diffraction analyses. Their electronic structures and mechanisms were investigated by density functional theory calculations.
报道了新型无金属白磷（P）活化方法。膦-硅亚烷基取代的二碳硼烷1，CB-SiP（CB = 邻位-C，C'-C₂B₁₀H₁₀，Si = PhC(tBuN)₂Si，P = P[N(tBu)CH₂]）以2:1的摩尔比活化白磷，生成含P链的物种2，而类似的双（硅亚烷基）取代化合物3，CB-Si₂以2:1的摩尔比与P反应，得到首个可分离的1,3-二磷杂-2,4-二硅丁二烯（含Si = P - Si = P）化合物4。对于后一反应，通过多核NMR光谱可观察到两种具有CB-SiP和CB-Si₂P核心的中间体。对化合物2和4进行了表征，包括单晶X射线衍射分析。通过密度泛函理论计算研究了它们的电子结构和反应机理。
