An Isolable Silicon Analogue of a Ketone that Contains an Unperturbed Si=O Double Bond

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.