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The 1 : 2 reaction of the imidazole‐based dithiolate (2) with GeCl2 • dioxane in THF/TMEDA gives 3, a TMEDA‐complexed dithiolene‐based germylene. Compound 3 is converted to monothiolate‐complexed (5) and N‐heterocyclic carbene‐complexed (7) germanium(II) dithiolene complexes via Lewis base ligand exchange. A bis‐dithiolene‐based germylene (8), involving a 3c–4e S‐Ge‐S bond, has also been synthesized through controlled hydrolysis of 7. The bonding nature of 3, 5, and 8 was investigated by both experimental and theoretical methods. [ABSTRACT FROM AUTHOR]

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]

Reaction of N-heterocyclic-carbene (NHC)-stabilized disilicon ( 1) with CuCl gave a carbene-stabilized disilicon-copper(I) chloride complex ( 2). The nature of the structure and bonding in 2 has been investigated by crystallographic, spectroscopic, and computational methods. The dynamic complexation behavior of 2 was experimentally explored by variable-temperature NMR analysis. [ABSTRACT FROM AUTHOR]