You can manage bookmarks using lists, please log in to your user account for this.
Media type:
E-Article
Title:
Intercepting the Disilene‐Silylsilylene Equilibrium
Contributor:
Stanford, Martin W.;
Schweizer, Julia I.;
Menche, Maximilian;
Nichol, Gary S.;
Holthausen, Max C.;
Cowley, Michael J.
imprint:
Wiley, 2019
Published in:Angewandte Chemie International Edition
Language:
English
DOI:
10.1002/anie.201810056
ISSN:
1433-7851;
1521-3773
Origination:
Footnote:
Description:
<jats:title>Abstract</jats:title><jats:p>The equilibrium between disilenes (R<jats:sub>2</jats:sub>Si=SiR<jats:sub>2</jats:sub>) and their silylsilylene (R<jats:sub>3</jats:sub>Si−SiR) isomers has previously been inferred but not directly observed, except in the case of the parent system H<jats:sub>2</jats:sub>Si=SiH<jats:sub>2</jats:sub>. Here, we report a new method to prepare base‐coordinated disilenes with hydride substituents. By varying the bulk of the coordinating base and other silicon substituents, we have been able to control the rearrangement of disilene adducts to their silylsilylene tautomers. Remarkably, 1,2 migration of a trimethylsilyl group is preferred over hydrogen migration. A DFT study of the reaction mechanism provides a rationale for the observed reactivity and detailed information on the bonding situation in base‐stabilized disilenes.</jats:p>