Labile Base-Stabilized Silyliumylidene Ions. Non-Metallic Species Capable of Activating Multiple Small Molecules

Several base-stabilized silyliumylidene ions (2 and 3) with different ligands were synthesized. Their behaviour appeared strongly dependent on the nature of ligand. Indeed, in contrast to the poorly reactive silyliumylidene ions 3 c,d stabilized by strongly donating ligands (DMAP, NHC), the silylene...

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Detalles Bibliográficos
Autores: Nougué, Raphaël, Takahashi, Shintaro, Dajnak, Aymeric, Maerten, Eddy, Baceiredo, Antoine, Saffon-Merceron, Nathalie, Branchadell, Vicenç|||0000-0003-3480-1669, Kato, Tsuyoshi|||0000-0001-9003-4455
Tipo de recurso: artículo
Fecha de publicación:2022
País:España
Institución:Universitat Autònoma de Barcelona
Repositorio:Dipòsit Digital de Documents de la UAB
Idioma:inglés
OAI Identifier:oai:ddd.uab.cat:282619
Acceso en línea:https://ddd.uab.cat/record/282619
https://dx.doi.org/urn:doi:10.1002/chem.202202037
Access Level:acceso abierto
Palabra clave:Frustrated lewis pairs
Silylenes
Silyliumylidene ions
Silylium ions
Small molecule activation
Descripción
Sumario:Several base-stabilized silyliumylidene ions (2 and 3) with different ligands were synthesized. Their behaviour appeared strongly dependent on the nature of ligand. Indeed, in contrast to the poorly reactive silyliumylidene ions 3 c,d stabilized by strongly donating ligands (DMAP, NHC), the silylene- and sulfide-supported one (2-H and 3 a) exhibits higher reactivity toward various small molecules. Furthermore, their capability to successively activate multiple small molecules was clearly demonstrated by processes involving successive reactions with silane/formamide, CO and H. Moreover, HBPin adduct of 3 a (8-C) catalyzes the hydroboration of pyridine. Of particular interest, silylene-supported silyliumylidene complex 2-H is one of the rare species able to activate two H molecules. Various base-stabilized silyliumylidene ions with different ligands were synthesized. Their behaviour appeared strongly dependent on the type of ligand. Indeed, in contrast to the poorly reactive silyliumylidenes stabilized by strongly donating ligands (DMAP, NHC), the sulfide-supported one (SMe) exhibits higher reactivity toward various small molecules. Furthermore, their capability to successively activate multiple small molecules was clearly demonstrated by processes involving successive reactions with silane/formamide, CO and H. Of particular interest, the silyliumylidene-silylene complex is one of the rare species able to activate two H molecules.