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

ABSTRACT: Mesoionic dithiolates [(MIDt^Ar )Li(LiBr)₂ (THF)₃ ] (MIDt^Ar ={SC(NDipp)}₂ CAr; Dipp=2,6-iPr₂ C₆ H₃ ; Ar=Ph 3 a, 3-MeC₆ H₄ (3-Tol) 3 b, 4-Me₂ NC₆ H₄ (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)GeCl₂ (L=1,4-dioxane) affords the germylene (MIDt^Ph )GeCl (5) featuring a three-coordinated Ge atom. 5 reacts with (L)GeCl₂ to give the Ge-Ge catenation product (MIDt^Ph )GeGeCl₃ (6). KC₈ 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.

SUBMITTER: Ebeler F 

PROVIDER: S-EPMC9323478 | biostudies-literature | 2022 Jun

REPOSITORIES: biostudies-literature