Carbene‐Stabilized Dithiolene (L0) Zwitterions.

A series of reactions between Lewis bases and an imidazole‐based dithione dimer (1) has been investigated. Both cyclic(alkyl)(amino)carbene (CAAC) (2) and N‐heterocyclic carbene (NHC) (4), in addition to N‐heterocyclic silylene (NHSi) (6), demonstrate the capability to cleave the sulphur–sulphur bonds in 1, giving carbene‐stabilized dithiolene (L0) zwitterions (3 and 5) and a spirocyclic silicon–dithiolene compound (7), respectively. The bonding nature of 3, 5, and 7 are probed by both experimental and theoretical methods. [ABSTRACT FROM AUTHOR]