Mesoionic Dithiolates (MIDts) Derived from 1,3-Imidazole-Based Anionic Dicarbenes (ADCs) |
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| Authors: | Falk Ebeler Dr Yury V Vishnevskiy Beate Neumann Dr Hans-Georg Stammler Priv-Doz?Dr Rajendra S Ghadwal |
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| Institution: | Molecular Inorganic Chemistry and Catalysis, Inorganic and Structural Chemistry, Center for Molecular Materials, Faculty of Chemistry, Universität Bielefeld, Universitätsstrasse 25, 33615 Bielefeld, Germany |
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| Abstract: | 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. |
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| Keywords: | carbenes dithiolene germanium lithium mesoionic |
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