A reactive Si4 cage: K(SitBu3)3Si4

A Free Silanide from Nucleophilic Substitution at Silicon(II)

“…The structure shows an ion pair with, at most, a weak interaction according to the long Si–K distance (3.8807(6) Å). Reported distances for contact ion pairs of Si − ⋅⋅⋅K + (18‐c‐6), range from 3.2911(16) to 3.9413(18) Å, featuring silanide 1 at the longer‐distance part of that spectrum, exceeded only by the cyclosilyl dianion reported by Fischer et al . The bicyclo[2.2.2]octane core possesses N−Si−N angles of 90.30(6)–91.14(4)°, consistent with a strong p character of the bonding orbitals and in agreement with the DFT‐predicted angles (see above).…”

Silicon clusters with six and seven unsubstituted vertices via a two-step reaction from elemental silicon

“…1a) and (Si t Bu 3 ) 3 Si 4 À (ref. 33) in whichagain via molecular precursors tri-substituted tetrahedral Si 4 clusters have been obtained. The idea of using Zintl anions as precursors for Si-rich molecules has constantly been pursued for more than two decades, nevertheless, many approaches were repeatedly discarded due to the high reducing properties of such silicides.…”

Transformative Si8R8 Siliconoids

“…In the chemical vapor deposition (CVD) process of elemental silicon, unsaturated silicon clusters with unsubstituted silicon vertices are considered as potential intermediates [6][7][8]. Recently, such kinds of unsaturated molecular silicon clusters are synthesized as isolable molecules [9][10][11][12][13][14][15][16][17][18][19][20][21][22] and termed "siliconoids" by Scheschkewitz et al [10]. The siliconoids show their characteristic distorted structures and large distribution of 29 Si nuclear magnetic resonances.…”

“…However, thermal transformation of siliconoids is still scarce. Scheschkewitz et al have reported thermal rearrangement, expansion, and contraction of Si 6 Tip 6 (Tip = 2,4,6-triisopropylphenyl) siliconoids [10,13,[15][16][17]22].…”