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Intercepting the Disilene‐Silylsilylene Equilibrium
Author(s) -
Stanford Martin W.,
Schweizer Julia I.,
Menche Maximilian,
Nichol Gary S.,
Holthausen Max C.,
Cowley Michael J.
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201810056
Subject(s) - tautomer , chemistry , reactivity (psychology) , adduct , hydride , base (topology) , trimethylsilyl , hydrogen , computational chemistry , medicinal chemistry , photochemistry , organic chemistry , medicine , mathematical analysis , alternative medicine , mathematics , pathology
The equilibrium between disilenes (R 2 Si=SiR 2 ) and their silylsilylene (R 3 Si−SiR) isomers has previously been inferred but not directly observed, except in the case of the parent system H 2 Si=SiH 2 . 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.