Mesoionic Dithiolates (MIDts) Derived from 1,3‐Imidazole‐Based Anionic Dicarbenes (ADCs)

Mesoionic dithiolates [(MIDt(Ar))Li(LiBr)(2)(THF)(3)] (MIDt(Ar)={SC(NDipp)}(2)CAr; Dipp=2,6‐iPr(2)C(6)H(3); Ar=Ph 3 a, 3‐MeC(6)H(4) (3‐Tol) 3 b, 4‐Me(2)NC(6)H(4) (DMP) 3 c) and [(MIDt(Ph))Li(THF)(2)] (4) are readily accessible (in≥90 % yields) as crystalline solids on treatments of anionic dicarbenes Li(ADC(Ar)) (2 a‐c) (ADC(Ar)={C(NDipp)(2)}(2)CAr) with elemental sulfur. 3 a‐c and 4 are monoanionic ditopic ligands with both the sulfur atoms formally negatively charged, while the 1,3‐imidazole unit bears a formal positive charge. Treatment of 4 with (L)GeCl(2) (L=1,4‐dioxane) affords the germylene (MIDt(Ph))GeCl (5) featuring a three‐coordinated Ge atom. 5 reacts with (L)GeCl(2) to give the Ge−Ge catenation product (MIDt(Ph))GeGeCl(3) (6). KC(8) reduction of 5 yields the homoleptic germylene (MIDt(Ph))(2)Ge (7). Compounds 3 a‐c and 4–7 have been characterized by spectroscopic studies and single‐crystal X‐ray diffraction. The electronic structures of 4–7 have been analyzed by DFT calculations.