Work

Reversible CO Insertion into the Si = Si Double Bond Enables a Disila-Bislactone Formation via Subsequent CO2 Addition

Year: 2025

Type: article

Abstract: High Resolution Image Download MS PowerPoint Slide Carbon monoxide inserts into the Si═Si double bond of an imino(silyl)disilene and tetra(silyl)disilene affording the corresponding 1,3-disilaallene oxides, characterized by NMR spectroscopy and X-ray crystallography and supported by quantum chemical calculations. In the case of imino(silyl)disilene, the CO insertion is less exergonic than for tetrasilyldisilene and, thus, is fully reversible in the presence of a CO trapping agent. The reaction mechanisms and reversibility facilitated by the imino-substituent were supported by quantum chemical calculations. The imino-supported 1,3-disilaallene oxide can react with low-pressure CO 2 to a disila-2,4-furandione; with increased CO 2 pressure, a 6-membered ring, disila-bislactone is formed. Their formation mechanisms were investigated via DFT calculations. Reaction of CO 2 with 1,3-disilaallene oxide was compared to the imino(silyl)disilene reacting with CO 2 in a [2 + 2] cycloaddition.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.5c07040

Authors: Fiona J. Kiefer, Arseni Kostenko, Richard Holzner, Shigeyoshi Inoue

Institution: Technical University of Munich

Language: English

Topic: Synthesis and characterization of novel inorganic/organometallic compounds

Subfield: Inorganic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funders: Deutsche Forschungsgemeinschaft, Wacker, European Research Council, Leibniz-Gemeinschaft