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- Title
Facile Synthesis of an Octagermacubane with Two Three‐Coordinate Germanium(0) Atoms and its Unique Radical Anion.
- Authors
Bashkurov, Roman; Kaushansky, Alexander; Tumanskii, Boris; Fridman, Natalia; Bravo‐Zhivotovskii, Dmitry; Apeloig, Yitzhak
- Abstract
Thermolysis of a 1 : 1 mixture of tris(di‐tert‐butylmethylsilyl)germane 9 and bis(di‐tert‐butylmethylsilyl)germane 17 at 100 °C produces unexpectedly octagermacubane 18, having two 3‐coordinate Ge0 atoms (40 % yield). 18 was characterized by X‐ray crystallography and it is a singlet biradical (according to DFT quantum mechanical calculations and the absence of an EPR signal). Reactions of 18 with CH2Cl2 and H2O yield the novel dichloro‐octagermacubane 24 and hydroxy‐octagermacubane 25, respectively. Reduction of 18 with tBuMe2SiNa in THF produces an isolable octagermacubane radical anion 26‐Na. Based on X‐ray crystallography, EPR spectroscopy and DFT quantum mechanical calculations, 26‐Na is classified as a Ge‐centered radical anion.
- Subjects
RADICAL anions; GERMANIUM; X-ray crystallography; ELECTRON paramagnetic resonance spectroscopy; ATOMS; THERMOLYSIS
- Publication
Angewandte Chemie, 2023, Vol 135, Issue 18, p1
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.202300847