New types of metal-free white phosphorus (P4) activation are reported. While the phosphine-silylene-substituted dicarborane 1, CB-SiP {CB = ortho-C,C´-C2B10H10, Si = PhC(tBuN)2Si, P = P[N(tBu)CH2]2}, activates white phosphorus in a 2:1 molar ratio to yield the P5-chain containing species 2, the analogous bis(silylene)-substituted compound 3, CB-Si2, reacts with P4 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-Si2P4 and CB-Si2P2 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.

https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202205358