Unexpected White Phosphorus (P<sub>4</sub>) Activation Modes with Silylene‐Substituted <i>o</i>‐Carboranes and Access to an Isolable 1,3‐Diphospha‐2,4‐disilabutadiene
Yun Xiong, Shicheng Dong, Shenglai Yao, Jun Zhu, Matthias Drieß
Abstract
Abstract New types of metal‐free white phosphorus (P 4 ) activation are reported. While the phosphine‐silylene‐substituted dicarborane 1 , CB‐ SiP (CB= ortho ‐C,C′‐C 2 B 10 H 10 , Si =PhC(tBuN) 2 Si, P =P[N(tBu)CH 2 ] 2 ), activates white phosphorus in a 2 : 1 molar ratio to yield the P 5 ‐chain containing species 2 , the analogous bis(silylene)‐substituted compound 3 , CB‐ Si 2 , reacts with P 4 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 2 P 4 and CB‐Si 2 P 2 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.