Ebeler Falk, Vishnevskiy Yury V, Neumann Beate, Stammler Hans-Georg, Ghadwal Rajendra S
Molecular Inorganic Chemistry and Catalysis, Inorganic and Structural Chemistry, Center for Molecular Materials, Faculty of Chemistry, Universität Bielefeld, Universitätsstrasse 25, 33615, Bielefeld, Germany.
Chemistry. 2022 Jun 1;28(31):e202200739. doi: 10.1002/chem.202200739. Epub 2022 Apr 13.
Mesoionic dithiolates [(MIDt )Li(LiBr) (THF) ] (MIDt ={SC(NDipp)} CAr; Dipp=2,6-iPr C H ; Ar=Ph 3 a, 3-MeC H (3-Tol) 3 b, 4-Me NC H (DMP) 3 c) and [(MIDt )Li(THF) ] (4) are readily accessible (in≥90 % yields) as crystalline solids on treatments of anionic dicarbenes Li(ADC ) (2 a-c) (ADC ={C(NDipp) } 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 (L=1,4-dioxane) affords the germylene (MIDt )GeCl (5) featuring a three-coordinated Ge atom. 5 reacts with (L)GeCl to give the Ge-Ge catenation product (MIDt )GeGeCl (6). KC reduction of 5 yields the homoleptic germylene (MIDt ) 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.
中离子二硫醇盐[(MIDt )Li(LiBr)(THF) ] (MIDt ={SC(NDipp)} CAr; Dipp=2,6-二异丙基苯基; Ar=苯基 3a、3-甲基苯基(3-甲苯基) 3b、4-甲基吡啶基(DMP) 3c)和[(MIDt )Li(THF) ] (4)在将阴离子二卡宾Li(ADC ) (2a - c) (ADC ={C(NDipp) } CAr)与元素硫反应时，很容易以结晶固体形式获得(产率≥90%)。3a - c和4是单阴离子双齿配体，两个硫原子形式上带负电荷，而1,3 -咪唑单元带形式上的正电荷。用(L)GeCl (L = 1,4 -二氧六环)处理4得到具有三配位Ge原子的亚锗烯(MIDt )GeCl (5)。5与(L)GeCl反应得到Ge - Ge键连产物(MIDt )GeGeCl (6)。用KC还原5得到均配亚锗烯(MIDt ) Ge (7)。化合物3a - c和4 - 7已通过光谱研究和单晶X射线衍射进行了表征。4 - 7的电子结构已通过DFT计算进行了分析。
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