The first isolated genuine germenyl lithiums (R 3 Si)(1-Ad)C=Ge(SiMetBu 2 )(Li•2 L) (R 3 Si = tBu 2 MeSi, L = THF (1 a), or L = 12-crown-4 (1 b) and R 3 Si = tBuMe 2 Si, L = THF (2 a), or L = 12-crown-4 (2 b)), were synthesized by reaction of the corresponding acyl germanes 3 and 4, respectively, with tBu 2 MeSiLi in THF at 70 °C. The novel 1 a and 2 b were characterized by NMR and UV/Vis spectroscopy, and also by X-ray crystallography (r(C=Ge) = 1.865 Å for 1 a and 1.877 Å for 2 b). Nucleophilic addition reaction of 1 a with MeI and a CÀ H insertion reactions to the C=Ge bond of 1 a, 2 a and 2 b, are reported. Oxidation of 1 a and 2 b (toluene, 230 K) produces the first persistent germenyl radicals (R 3 Si)(1-Ad)C=Ge * -(SiMetBu 2 ) (R 3 Si = tBu 2 MeSi (13 a), R 3 Si = tBuMe 2 Si (13 b)), which were characterized by EPR spectroscopy (t 1/2 � 30 min at 230 K, g = 2.029, a av ( 73 Ge) is 55.0G for 13 a and 60.2G for 13 b). The experimental EPR parameters and DFT calculations indicate that 13 a and 13 b have a strongly bent structure at Ge (calc. ∡(C=GeÀ Si) = 136.7°(13 a), 135.9°(13 b)), and that the unpaired electron has a substantial s-character.

The first isolated genuine germenyl lithiums (R3Si)(1‐Ad)C=Ge(SiMetBu2)(Li⋅2 L) (R3Si=tBu2MeSi, L=THF (1 a), or L=12‐crown‐4 (1 b) and R3Si=tBuMe2Si, L=THF (2 a), or L=12‐crown‐4 (2 b)), were synthesized by reaction of the corresponding acyl germanes 3 and 4, respectively, with tBu2MeSiLi in THF at 70 °C. The novel 1 a and 2 b were characterized by NMR and UV/Vis spectroscopy, and also by X‐ray crystallography (r(C=Ge)=1.865 Å for 1 a and 1.877 Å for 2 b). Nucleophilic addition reaction of 1 a with MeI and a C−H insertion reactions to the C=Ge bond of 1 a, 2 a and 2 b, are reported. Oxidation of 1 a and 2 b (toluene, 230 K) produces the first persistent germenyl radicals (R3Si)(1‐Ad)C=Ge⋅‐(SiMetBu2) (R3Si=tBu2MeSi (13 a), R3Si=tBuMe2Si (13 b)), which were characterized by EPR spectroscopy (t1/2≈30 min at 230 K, g=2.029, aav(73Ge) is 55.0G for 13 a and 60.2G for 13 b). The experimental EPR parameters and DFT calculations indicate that 13 a and 13 b have a strongly bent structure at Ge (calc. ∡(C=Ge−Si)=136.7° (13 a), 135.9° (13 b)), and that the unpaired electron has a substantial s‐character.