[1 + 2] Cycloaddition of a Cyclic (Alkyl)(amino)silylene and a Disilyne Providing a 3-Aminocyclotrisilene

Abstract

Despite the notable progress in the chemistry of cycloaddition reactions of silylenes toward unsaturated bonds, such reactions toward a Si Si triple bond remain unknown. Herein, we report [1 + 2] cycloaddition of a cyclic (alkyl)(amino)silylene (1) and a dialkyldisilyne (2) to form a 3aminocyclotrisilene (3). Cyclotrisilene 3 adopts a slightly cis-bent geometry with a relatively long SiSi double bond in the solid state, suggesting a π(SiSi)−σ*(Si−N) interaction. Thermolysis of 3 regenerated silylene 1, which was trapped as Et 3 SiH and toluene adducts at high temperatures.

Conformationally Switchable Silylone: Electron Redistribution Accompanied by Ligand Reorientation around a Monatomic Silicon

“…The aforementioned studies along with the absence of bicyclo[1.1.0]­tetrasil-1(3)-ene 13b and silylone 1 suggest that the ligand exchange reaction should proceed by a stepwise mechanism and likely via disilavinylidene intermediate 14a rather than 14b . The presence of the thermally stable CAASi 3 or the strong ylidene character of 1 and 2 should be the major driving force for the reaction to proceed . Similar silicon transfer reactions were individually reported by Roesky and Robinson’s group, but both involve the oxidation of the central silicon atom during the reactions.…”

Recent advances of group 14 dimetallenes and dimetallynes in bond activation and catalysis

“…Like in multiply bonded transition-metal M–M and M–C compounds, 36–38 cycloaddition is an often-observed reaction for dimetallenes and dimetallynes. 16,39–53 Moreover, when going down the group these effects get even stronger, with more exposed lone pairs and decreasing E–E bond energies. For dimetallynes, singlet diradical character can be seen as a mesomeric structure and in reaction, respectively.…”

Metal‐free Kinugasa reaction catalyzed by external electric field

“…[ 34 ] Each stationary point and TS along the reaction profile were confirmed by intrinsic reaction coordinate (IRC) calculations and harmonic frequency calculations. The bond‐forming axis, namely, the axis along which the two R 2 N + O − C(H) and R 3 CC(R [ 1 ] ) C‐C bonds are formed in the [3 + 2] cycloaddition, is considered as the reaction axis (see Scheme 1). The reactant complexes and TSs are oriented along this axis (termed as X axis henceforth).…”