Complex of Silylene with Nitrogen: A Combined Matrix‐Spectroscopic and Density Functional Theory Study

Abstract

The quest for a new and productive route to matrix-isolated silylene 1 has led to the observation that the presence of nitrogen is favorable, as under such conditions 1 is stabilized by formation of a donor-acceptor complex 1 x N2. Either matrix photolysis of diazidosilane or pulsed high-vacuum flash pyrolysis of 1,1,1-trimethyldisilane, followed by condensation of the products with nitrogen at 10 K, were applied as synthetic procedures. In a similar manner, complex 1 x CO can be generated. The results are supported by isotopic-labeling studies. The structural elucidation of the new species is based on the comparison of experimental IR and UV/Vis spectra with data from density functional theory calculations.

Flash‐Vakuumpyrolyse – Techniken und Reaktionen

“…[187] Ebenso wurde 1-Silacyclopropenyliden durch gepulste Pyrolyse von 1,1-Dimethyl-2-ethinyldisilangeneriert, und es wurde gezeigt, dass es in der Ar-Matrix photochemisch eine wechselseitige Umwandlung in 1-Silapropadienylidenund 1-Silapropargylen eingeht. [189] Eine von Ellison, Nimlos,R adziszewski et al beschriebene Pulspyrolysedüse wurde eingesetzt, um aus Phenyliodid das detaillierte IR-Spektrum des Phenylradikals,C 6 H 5 C,inAr-Matrix bei 10 Kzuerhalten [Gl. (49)],o bgleich herkçmmliche FVP hier ohne Erfolg war.…”

“…(49)],o bgleich herkçmmliche FVP hier ohne Erfolg war. [189] Eine von Ellison, Nimlos,R adziszewski et al beschriebene Pulspyrolysedüse wurde eingesetzt, um aus Phenyliodid das detaillierte IR-Spektrum des Phenylradikals,C 6 H 5 C,inAr-Matrix bei 10 Kzuerhalten [Gl. (50)].…”

Coordination of N2and Other Small Molecules to the Phosphorus Centre of RPW(CO)5: A Theoretical Study on the Janus Facets of the Stabilization/Activation Problem

“…Concerning the fixation of CO by non‐metal main group element group 14 centres, related results were reported for a CAAC derivative, yielding a bent ketene, and for silylene H 2 Si forming a Lewis acid base complex with CO ]12] as matrix isolation studies have shown. Information on reactions of similar complexes of divalent carbon and silicon species with N 2 is even more scarce, despite the fact that diazoalkanes have a rich chemistry and H 2 CN 2 has been known since 1894 …”

“…[9] Maybe the most strikingexample for this paralleled transition-metal coordination chemistry was the outcome of ab ondinga nalysis of neutral complexes having CO kC-bound to ap hosphorus centre. [5,10] Concerningt he fixation of CO by non-metal main group element group 14 centres,r elated results were reported for aC AAC derivative, yieldingabent ketene, [11] and for silylene H 2 Si formingaLewisa cid base complex with CO ]12] as matrix isolation studies have shown.I nformationo nr eactions of similarc omplexes of divalent carbon and silicon species with N 2 is even more scarce, [12] despite the fact that diazoalkanes [13] have ar ich chemistry and H 2 CN 2 has been known since 1894. [14] From ad ifferentp erspective, there was al ongstanding targetinthe chemistry of neutralterminal phosphinidenecomplexes ID the stabilization of such fleeting neutral intermediates.…”

Flash Vacuum Pyrolysis: Techniques and Reactions

“…( 49)], where conventional FVP failed. [189] This article is protected by copyright. All rights reserved…”