An Isolable Three‐Coordinate Germanone and Its Reactivity. Issue 64 (5th October 2021)

• Record Type: Journal Article
• Authors: Zhao, Xuan‐Xuan; Szilvási, Tibor; Hanusch, Franziska; Inoue, Shigeyoshi
• Is Part Of: Chemistry. Volume 27:Issue 64(2021)
• Page Start: 15914
• Page End: 15917
• Publication Date: 2021-10-05
• Subjects: carbonyls -- germanone -- N-heterocyclic imines -- O-atom transfer -- small molecule activation; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202102972
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: A rare three‐coordinate germanone [IPrN]2 Ge=O (IPrN=bis(2, 6‐diisopropylphenyl)imidazolin‐2‐imino) was successfully isolated. The germanone has a rather high thermal stability in arene solvent, and no detectable change was observed at 80 °C for at least one week. However, high thermal stability of [IPrN]2 Ge=O does not prevent its reactivity toward small molecules. Structural analysis and initial reactivity studies revealed the highly polarized nature of the terminal Ge=O bond. Besides, the addition of phenylacetylene, as well as O‐atom transfer with 2, 6‐dimethylphenyl isocyanide make it a mimic of nucleophilic transition‐metal oxides. Mechanism for O‐atom transfer reaction was investigated via DFT calculations, which revealed that the reaction proceeds via a [2+2] cycloaddition intermediate. Abstract : A rare three‐coordinate germanone : bis(imino)germanone [IPrN]2 Ge=O (IPrN=bis(2, 6‐diisopropylphenyl)imidazolin‐2‐imino) was successfully isolated. Initial reactivity studies combined with experimental and computational bonding analysis revealed highly polarized nature of the terminal Ge=O bond. Moreover, transition metal oxide‐like reactivity has been observed for the addition of phenylacetylene, as well as O‐atom transfer with 2, 6‐dimethylphenyl isocyanide.