Open-Shell Germylene Stabilized by a Phenalenyl-Based Ligand
Takuya Kodama, K. Uchida, Chihiro Nakasuji, Ryohei Kishi, Yasutaka Kitagawa, Mamoru Tobisu
Abstract
An open-shell germylene 1 stabilized by a phenalenyl-based bidentate ligand was synthesized and characterized. Because of the high thermal stability originating from spin delocalization over the phenalenyl moiety, it was possible to isolate compound 1 in crystalline form by sublimation at ca. 300 °C. Electron spin resonance (ESR) spectra, crystallographic analysis, theoretical calculations, and reactivities with carbon radicals suggest that the spin of 1 is distributed on the phenalenyl moiety, while 1 reacted with C 2 Cl 6, PhSSPh, and p -benzoquinone at the germanium center to form Ge–E (E = Cl, S, O) bonds. Furthermore, compound 1 is featured by its reactivity as a “formal germylyne”, which allows for the formation of three new σ-bonds or one σ-bond with metal complexation on the germanium center.