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

Ebeler, Falk; Vishnevskiy, Yury V.; Neumann, Beate; Stammler, Hans‐Georg; Ghadwal, Rajendra S.

Mesoionic dithiolates [(MIDtAr)Li(LiBr)2(THF)3] (MIDtAr={SC(NDipp)}2CAr; Dipp=2,6‐iPr2C6H3; Ar=Ph 3 a, 3‐MeC6H4 (3‐Tol) 3 b, 4‐Me2NC6H4 (DMP) 3 c) and [(MIDtPh)Li(THF)2] (4) are readily accessible (in≥90 % yields) as crystalline solids on treatments of anionic dicarbenes Li(ADCAr) (2 a‐c) (ADCAr={C(NDipp)2}2CAr) 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)GeCl2 (L=1,4‐dioxane) affords the germylene (MIDtPh)GeCl (5) featuring a three‐coordinated Ge atom. 5 reacts with (L)GeCl2 to give the Ge−Ge catenation product (MIDtPh)GeGeCl3 (6). KC8 reduction of 5 yields the homoleptic germylene (MIDtPh)2Ge (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.

DITHIOLATES; CRYSTALS; ELECTRONIC structure; X-ray diffraction; SULFUR

Chemistry - A European Journal, 2022, Vol 28, Issue 31, p1

0947-6539

Academic Journal

10.1002/chem.202200739