A neutral crystalline imino-substituted silyl radical.

The neutral three-coordinated imino(silyl)silyl radical was isolated from the reaction of N-heterocyclic iminosilicon tribromide (IBuN-SiBr) with NaSiBuMe. The radical was fully characterized by X-ray crystallography and electron paramagnetic resonance spectroscopy and supported by quantum chemical calculations.

Cataluminescence in Er-Substituted Perovskites.

Thermophotovoltaic devices have promising applications for energy conversion. However, current conversion efficiency of chemical energy to light is very low, limited by the competing process of heat dissipation released as black body radiation. From a fundamental point of view, the direct conversion of chemical energy into light without this detour is possible.

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.

Silylated silicon-carbonyl complexes as mimics of ubiquitous transition-metal carbonyls.

Transition-metal-carbonyl complexes are common organometallic reagents that feature metal-CO bonds. These complexes have proven to be powerful catalysts for various applications. By contrast, silicon-carbonyl complexes, organosilicon reagents poised to be eco-friendly alternatives for transition-metal carbonyls, have remained largely elusive.

DMAP-stabilized bis(silyl)silylenes as versatile synthons for organosilicon compounds.

DMAP-stabilized silylenes 1a-c are obtained from the reductive debromination of the corresponding dibromosilanes in the presence of DMAP. Their distinctly different thermal isomerization reactions C-H bond activation, dearomative ring expansion and silyl migration are discussed. Furthermore, complexes 1 dissociate at elevated temperatures, providing the corresponding free silylenes , which are even capable of single-site activation of H.

Disilene-Silylene Interconversion: A Synthetically Accessible Acyclic Bis(silyl)silylene.

Silylenes have recently shown fascinating reactivity patterns, which are normally observed almost exclusively for transition-metal complexes. In particular, very reactive representatives are considered to be promising candidates, which may become powerful and economical alternatives for catalytic applications in the future. Here, we present the isolation of an equilibrium mixture consisting of a tetrasilyldisilene and its isomeric bis(silyl)silylene, the first isolable silylene of this type.

NHCs in Main Group Chemistry.

Since the discovery of the first stable N-heterocyclic carbene (NHC) in the beginning of the 1990s, these divalent carbon species have become a common and available class of compounds, which have found numerous applications in academic and industrial research. Their important role as two-electron donor ligands, especially in transition metal chemistry and catalysis, is difficult to overestimate. In the past decade, there has been tremendous research attention given to the chemistry of low-coordinate main group element compounds.

Polythioethers by thiol-ene click polyaddition of α,ω-alkylene thiols.

The straightforward synthesis of a series of poly(thioether)s by photoinduced thiol-ene click polyaddition of α,ω-alkylene thiols is reported. It is found that linear and telechelic poly(thioether)s can be directly obtained from α,ω-alkylene thiols with, for example, alkyl chain length of m = 1,2,3, and 9. The reaction proceeds without additives such as (radical) initiators or metal compounds and can simply be carried out by UV-irradiation of the bulk monomer or monomer solution.