Stabilisation of the [SiH₆]²⁻ Anion within a Supramolecular Assembly

The hypercoordinate [SiH 6 ] 2− anion is not stable in solution. Here, we report the room temperature, solution stable molecular [SiH 6 ] 2− complex, [{KCa( NON )(OEt 2 )} 2 ][SiH 6 ] ( NON =4,5‐bis(2,6‐diisopropylanilido)‐2,7‐di‐tert‐butyl‐9,9‐dimethyl‐xanthene)), where the [SiH 6 ] 2− anion is stabilised within a supramolecular assembly that mimics the solid‐state environment of the anion in the lattice of K 2 SiH 6 . Solution‐state reactivity of the complex towards carbon monoxide, benzaldehyde, azobenzene and acetonitrile is reported, yielding a range of reduction and C−C coupled products.