Synthesis of Genuine Germenyl Lithiums and the First Persistent Germenyl Radicals

• Published in: Angewandte Chemie International Edition 2022-06, Vol.61 (25), p.e202202452-n/a
• Main Authors: Goldshtein, Yulia, Glagovsky, Yuri, Tumanskii, Boris, Fridman, Natalia, Bravo‐Zhivotovskii, Dmitry, Apeloig, Yitzhak
• Format: Article
• Language: English
• Subjects: Anions; Chemical synthesis; Communication; Communications; Crystallography; DFT calculations; EPR Spectroscopy; Germanium; Germenyl Radicals; NMR; Nuclear magnetic resonance; Oxidation; Radicals; Silicon; Spectroscopy; Spectrum analysis; Toluene
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202202452

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. Two novel germenyl lithiums (1 a and 2 b), having a genuine C=Ge bond and substituents with mild electronic effects, were synthesized and structurally characterized. Further oxidation of compounds 1 a (or 2 b) produced the first persistent germenyl radicals 13 a (or 13 b) which were characterized by EPR spectroscopy and DFT calculations.