Metal‐Free Activation of EH₃ (E=P, As) by an Ylide‐like Silylene and Formation of a Donor‐Stabilized Arsasilene with a HSiAsH Subunit

Twice, and faster: Reaction of the zwitterionic silylene 1 with AsH3 occurs stepwise at ambient temperature to give the first crystalline, donor-stabilized arsasilene 3 via its 1,1-addition product (silylarsane 2). In contrast, the activation of PH3 by 1 merely leads to the phosphorus analogue of 2. The strikingly different metal-free activation of the series of Group 15 hydrides EH3 (E=N, P, As) by 1 was rationalized with DFT calculations. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.