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- Title
Transition-Metal-Mediated Cleavage of Fluoro-Silanes under Mild Conditions.
- Authors
Kameo, Hajime; Kawamoto, Tatsuya; Sakaki, Shigeyoshi; Bourissou, Didier; Nakazawa, Hiroshi
- Abstract
Si−F bond cleavage of fluoro-silanes was achieved by transition-metal complexes under mild and neutral conditions. The Iridium-hydride complex [Ir(H)(CO)(PPh3)3] was found to readily break the Si−F bond of the diphosphine- difluorosilane {( o-Ph2P)C6H4}2Si(F)2 to afford a silyl complex [{[ o-( iPh2P)C6H4]2(F)Si}Ir(CO)(PPh3)] and HF. Density functional theory calculations disclose a reaction mechanism in which a hypervalent silicon species with a dative Ir→Si interaction plays a crucial role. The Ir→Si interaction changes the character of the H on the Ir from hydridic to protic, and makes the F on Si more anionic, leading to the formation of Hδ+⋅⋅⋅Fδ− interaction. Then the Si−F and Ir−H bonds are readily broken to afford the silyl complex and HF through σ-bond metathesis. Furthermore, the analogous rhodium complex [Rh(H)(CO)(PPh3)3] was found to promote the cleavage of the Si−F bond of the triphosphine-monofluorosilane {( o-Ph2P)C6H4}3Si(F) even at ambient temperature.
- Subjects
TRANSITION metal compounds synthesis; IRIDIUM compound synthesis; SILANE compounds; CHEMICAL synthesis; PHOSPHINE synthesis; SCISSION (Chemistry); LIGANDS (Chemistry); DENSITY functional theory
- Publication
Chemistry - A European Journal, 2016, Vol 22, Issue 7, p2370
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201504455