Fluorosilane Activation by Pd/Ni→Si–F→Lewis Acid Interaction: An Entry to Catalytic Sila-Negishi Coupling

Hajime Kameo (1) , Hiroki Yamamoto , Koki Ikeda , Tomohito Isasa , Shigeyoshi Sakaki , Hiroyuki Matsuzaka , Yago García-Rodeja , Karinne Miqueu (2) , Didier Bourissou (3)

1 Division of Applied Chemistry, Graduate School of Engineering, Osaka University
2 IPREM - Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux
3 LHFA - Laboratoire Hétérochimie Fondamentale et Appliquée

A new mode of bond activation involving M→Z interactions is disclosed. Coordination to transition metals as σ-acceptor ligands was found to enable the activation of fluorosilanes, opening the way to the first transition-metal-catalyzed Si-F bond activation. Using phosphines as directing groups, sila-Negishi couplings were developed by combining Pd and Ni complexes with external Lewis acids such as MgBr2. Several key catalytic intermediates have been authenticated spectroscopically and crystallographically. Combined with DFT calculations, all data support cooperative activation of the fluorosilane via Pd/Ni→Si-F→Lewis acid interaction with conversion of the Z-type fluorosilane ligand into an X-type silyl moiety.

Domaines: Matériaux; Polymères; Chimie théorique et/ou physique; Chimie analytique

Hajime Kameo, Hiroki Yamamoto, Koki Ikeda, Tomohito Isasa, Shigeyoshi Sakaki, et al.. Fluorosilane Activation by Pd/Ni→Si–F→Lewis Acid Interaction: An Entry to Catalytic Sila-Negishi Coupling. Journal of the American Chemical Society, 2020, 142 (33), pp.14039-14044. ⟨10.1021/jacs.0c04690⟩. ⟨hal-02927518⟩