PUB - Publikationen an der Universität Bielefeld

Mesoionic dithiolates [(MIDt Ar )Li(LiBr) 2 (THF) 3 ] (MIDt Ar = {SC(NDipp)} 2 CAr; Dipp = 2,6- i Pr 2 C 6 H 3 ; Ar = Ph 3a , 3-MeC 6 H 4 (3-Tol) 3b , 4-Me 2 NC 6 H 4 (DMP) 3c ) and [(MIDt Ph )Li(THF) 2 ] ( 4 ) are readily accessible (in ≥ 90% yields) as crystalline solids on treatments of anionic dicarbenes Li(ADC Ar ) ( 2a-c ) (ADC Ar = {C(NDipp) 2 } 2 CAr) with elemental sulfur. 3a-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 3a-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. © 2022 Wiley-VCH GmbH.