Selective Route to Stable Silicon-Boron Radicals and Their Corresponding Cations.

Herein, we report on a facile and selective one-pot synthetic route to silicon-boron radicals. Reduction of BrBTip (Tip = 2,4,6-PrCH) with KC in the presence of LSi-R affords LSi(Bu)-B(Br)Tip () and LSi(N(TMS))-B(Br)Tip () [L = PhC(NBu)]. These first examples of silicon-boron isolated radical species feature spin density on the silicon and boron atoms.

1-Aza-2,4-disilabicyclo[1.1.0]butanes with Superelongated C-N σ-Bonds.

Two silylene molecules oxidatively react under formal [1 + 2 + 1]-cycloaddition to the C≡N bond of nitriles to yield 1-aza-2,4-disilabicyclo[1.1.0]butanes (L)(Cl)Si[μ-η-NC(-RCH)]Si(Cl)(L) (L = PhC(NBu), R = CF (), F (), Cl (), Br ()).