Trisilaallene is a subclass of silene derivatives where a central silicon atom forms double bonds with each of two terminal silicon atoms, with the generic formula R2Si=Si=SiR2. Trisilaallene is a silicon-based analog of an allene, but their chemical properties are markedly different.
Synthesis
The first isolable trisilaallene compound was reported by Kira et al. in 2003, synthesized by reductive dehalogenation of tetrachlorosilane using potassium graphite. This tetraalkyl-substituted trisilallene showed thermal stability up to its melting point around 200 °C, but decomposed in contact with air. Its remarkable stability is attributable to bulky substituents providing kinetic protection at the terminal silicon atoms. The 29Si-NMR shifts of the central silicon and terminal silicon atoms were observed at 157.0 ppm and 196.9 ppm respectively. Two Si=Si bond lengths were determined to be 2.177 Å and 2.188 Å by X-ray crystallography, which are within the typical range of Si=Si double bonds.
Sekiguchi et al. synthesized a silyl-substituted trisilaallene from a reaction between a N-heterocyclic carbene (NHC) adduct of SiCl2 and 1,1-dilithiosilane (t-Bu2MeSi)2SiLi2. Although crystallographic analysis of the product was not successful, the formation of trisilaallene was confirmed by 1H-, 13C-, and 29Si-NMR spectroscopy, high-resolution mass spectrometry (HRMS), and reactivity study. The low electronegativity of silyl substituents compared to alkyl substituents resulted in a more upfield 29Si-NMR shift for the terminal silicon atoms (44.6 ppm) and a downfield shift for the central atom (418.5 ppm).
Structure and bonding
Geometry
In contrast to its linear carbon analog, trisilaallene is characterized by bent geometry. For example, Kira's trisilaallene had a Si=Si=Si bond angle of 136.5º. While the bulky and electropositive silyl ( tBu2MeSi-) substituents widened the bond angle to 164.3º (calculated), no linear trisilaallene has been reported yet. The two planes that each terminal silicon atom and attached substituents lie on tend to be perpendicular to each other, which is analogous with allene. The central silicon atom shows fluxional behavior in that its relative position varies with respect to the substituents planes, and the distribution of resultant isomers depends on the temperature.
The bent structure of trisilaallene is explained by the second-order Jahn-Teller distortion. Unlike the 2s and 2p orbitals of carbon, where the orbital radii of maximum electron density are similar, the 3s orbital of silicon is significantly smaller than 3p orbitals (rnp– rns= -0.2 pm for n = 2 and > 20 pm for n > 2). Therefore, the σ-overlap between the 3s orbital of the central silicon atom and a set of 3pz orbitals of the terminal atoms (when z-axis is the molecular axis) is poor compared to in allene, resulting in a relatively low-lying σ*-orbital. The energy gap between σ*-orbital and π-orbitals originated from 3px and 3py orbitals is small enough to induce considerable mixing between the σ*-orbital and one of the π-orbitals with appropriate symmetry. This orbital mixing removes degeneracy between the two π-orbitals, accompanied by geometric distortion.
The ab initio and density functional theory (DFT) calculations predict that Si3R4 molecules with smaller substituents (R = H or Me) adopt zwitterionic structures with C2v or Cs symmetry and with drastically smaller bond angles (~70º for R = H, ~90º for R = Me). However, the steric congestion required for isolation prevent these highly bent structures.