Imino(silyl)disilenes: application in versatile bond activation, reversible oxidation and thermal isomerization.

Two novel disilenes of type ABSi[double bond, length as m-dash]SiAB bearing N-heterocyclic imino (A = NItBu) and trialkylsilyl (B = SitBu31, B = SitBu2Me 2) groups are reported. The reduced steric demand in 2 results in a highly stable, nonetheless flexible system, wherefore (E/Z) isomerization is observed from room temperature up to 90 °C. The proposed isomerization mechanism proceeds via monomeric silylenes in line with experimental results.

Oxidation reactions of a versatile, two-coordinate, acyclic iminosiloxysilylene.

Due to their outstanding reactivity, acyclic silylenes have emerged as attractive organosilicon alternatives for transition metal complexes on the way to metal-free catalysis. However, exploration of their reactivity is still in its infancy, as only a few derivatives of this unique compound class have been isolated so far. Here, we present the results of an extensive reactivity investigation of the previously reported acyclic iminosiloxysilylene 1.

Precise Activation of Ammonia and Carbon Dioxide by an Iminodisilene.

The activation of NH and CO is still an ambitious target for multiply bonded sub-valent silicon compounds. Now, the precise splitting of the N-H bond of ammonia by (Z)-imino(silyl)disilene 1 to give trans-1,2-adduct 2 a at low temperatures (-78 °C) is presented. According to DFT calculations, the stereospecific hydroamination follows a similar mechanism as the recently reported anti-addition of H to the Si=Si bond of 1.

Chalcogen-atom transfer and exchange reactions of NHC-stabilized heavier silaacylium ions.

Heavier analogues of silaacylium ions 2-4 ([m-TerSiE(NHC)]Cl; m-Ter = 2,6-MesCH; Mes = 2,4,6-MeCH; 2 (E = S), 3 (E = Se), 4 (E = Te)) were synthesized by the reaction of the NHC-stabilized silyliumylidene cation 1 with elemental chalcogens. Fascinating regeneration of 1 from the reaction of 2-4 with AuI was achieved, as successful recovery of a parent Si(ii) species from a silachalcogen Si(iv) compound. Furthermore, unique chalcogen exchange reactions from 4 → 3 → 2 were observed in line with the calculated silicon-chalcogen bond energies.

Silicon and Oxygen's Bond of Affection: An Acyclic Three-Coordinate Silanone and Its Transformation to an Iminosiloxysilylene.

A long-term dream comes true: An acyclic, neutrally charged silanone at last! Here, we report on the first examples of isolable acyclic, neutral, three-coordinate silanones 2 with indefinite stability as solids and lifetimes in solution of up to 2 days. The electronic properties of the Si═O bond were investigated via DFT calculations and revealed the π-donating N-heterocyclic imino (NHI) and σ-donating silyl groups as key factors for their enhanced stability. Besides initial reactivity studies of 2 toward CO and methanol, different isomerization pathways depending on the silyl substitution pattern were found.

Twist of a Silicon-Silicon Double Bond: Selective Anti-Addition of Hydrogen to an Iminodisilene.

Hydrogenation of alkenes with C═C bonds is a ubiquitous reaction in organic chemistry. However, this transformation remains unknown for heavier counterparts, disilenes with Si═Si bonds. Here we report the isolation of (Z)-diiminodisilyldisilene 2 featuring a highly trans-bent and twisted structure and the longest silicon-silicon double bond reported to date.

From Si(II) to Si(IV) and Back: Reversible Intramolecular Carbon-Carbon Bond Activation by an Acyclic Iminosilylene.

Reversibility is fundamental for transition metal catalysis, but equally for main group chemistry and especially low-valent silicon compounds, the interplay between oxidative addition and reductive elimination is key for a potential catalytic cycle. Herein, we report a highly reactive acyclic iminosilylsilylene 1, which readily performs an intramolecular insertion into a C═C bond of its aromatic ligand framework to give silacycloheptatriene (silepin) 2. UV-vis studies of this Si(IV) compound indicated a facile transformation back to Si(II) at elevated temperatures, further supported by density functional theory calculations and experimentally demonstrated by isolation of a silylene-borane adduct 3 following addition of B(CF).