An Isolable Silicon Analogue of a Ketone that Contains an Unperturbed Si=O Double Bond. (18th June 2019)

• Record Type: Journal Article
• Authors: Kobayashi, Ryo; Ishida, Shintaro; Iwamoto, Takeaki
• Is Part Of: Angewandte Chemie. Volume 131:Number 28(2019)
• Page Start: 9525
• Page End: 9528
• Publication Date: 2019-06-18
• Subjects: Carbonylverbindungen -- Ketone -- Si=O-Bindungen -- Silanone -- Silicium; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201905198
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Despite tremendous efforts to synthesize isolable compounds with an Si=O bond, silicon analogues of ketones that contain an unperturbed Si=O bond have remained elusive for more than 100 years. Herein, we report the synthesis of an isolable silicon analogue of a ketone that exhibits a three‐coordinate silicon center and an unperturbed Si=O bond, thus representing the first example of a genuine silanone. Most importantly, this silanone does not require coordination by Lewis bases and acids and/or the introduction of electron‐donating groups to stabilize the Si=O bond. The structure and properties of this unperturbed Si=O bond were examined by a single‐crystal X‐ray diffraction analysis, NMR spectroscopy, and theoretical calculations. Bimolecular reactions revealed high electrophilicity on the Si atom and high nucleophilicity on the O atom of this genuine Si=O bond. Abstract : Sehen Si her ! Das erste Beispiel eines echten Silanons, eines isolierbaren Silicium‐Analogons eines Ketons mit ungestörter Si=O‐Bindung, wurde synthetisiert. Struktur und Eigenschaften wurden mittels Einkristall‐XRD‐Analyse, NMR‐Spektroskopie und theoretischen Studien untersucht. Bimolekulare Reaktionen zeigen eine hohe Elektrophilie am Si‐Atom und eine hohe Nukleophilie am O‐Atom der Si=O‐Bindung.