Abstract: | The two hypersilylcuprates LiCu2Hyp3 ( 2 ) and [Li7(OtBu)6][Cu2Hyp3] ( 3 ) (Hyp = Si(SiMe3)3) were synthesized by reactions of unsolvated lithium hypersilanide, LiHyp with hypersilylcopper and CuOtBu, respectively. Both contain the novel A‐frame trihypersilyldicuprate anion [Cu2Hyp3]–. In the former case a molecular compound is produced containing intimate ion pairs. In the latter case the cuprate anion and the unique large [Li7(OtBu)6]+ cation form a salt‐like compound, only sparingly soluble in unpolar solvents. According to NBO analyses the bonding within the trihypersilyldicuprate moiety is best described by interaction of a bridging lewis‐basic hypersilanide anion with two lewis‐acidic hypersilyl copper fragments. |