Labile Base-Stabilized Silyliumylidene Ions. Non-Metallic Species Capable of Activating Multiple Small Molecules
Nougué, Raphaël (Université de Toulouse)
Takahashi, Shintaro (Université de Toulouse)
Dajnak, Aymeric (Université de Toulouse)
Maerten, Eddy (Université de Toulouse)
Baceiredo, Antoine (Université de Toulouse)
Saffon-Merceron, Nathalie (Institut de Chimie de Toulouse)
Branchadell Gallo, Vicenç (Universitat Autònoma de Barcelona. Departament de Química)
Kato, Tsuyoshi (Université de Toulouse)

Date:	2022
Abstract:	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.
Grants:	European Commission 306658 Agencia Estatal de Investigación PID2020-116861GB-I00
Rights:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, i la comunicació pública de l'obra, sempre que no sigui amb finalitats comercials, i sempre que es reconegui l'autoria de l'obra original. No es permet la creació d'obres derivades.
Language:	Anglès
Document:	Article ; recerca ; Versió publicada
Subject:	Frustrated lewis pairs ; Silylenes ; Silyliumylidene ions ; Silylium ions ; Small molecule activation
Published in:	Chemistry, Vol. 28, Issue 70 (December 2022) , art. e202202037, ISSN 1521-3765

DOI: 10.1002/chem.202202037
PMID: 36074891

15 p, 1.9 MB

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