β-SiH rich zinc silyl compounds: Reductive elimination and β-hydrogen abstraction

Add time:08/22/2019    Source:sciencedirect.com

The two-coordinate compound Zn{Si(SiHMe2)3}2 (1) is generated by the reaction of ZnCl2 and 2 equiv. of KSi(SiHMe2)3, but this species undergoes reductive elimination to produce (Me2HSi)3Si–Si(SiHMe2)3 and metallic zinc over 48 h at room temperature. The transient disilylzinc compound is stabilized by a neutral N-heterocyclic carbene (NHC) 1,3-di-t-butylimidazol-2-ylidene (ImtBu) or the chelating N-donor ligands 1,2-dipyrrolidinoethane (dpe) or 2,2′-bipyridine (bipy). The one-bond silicon-hydrogen coupling constants (1JSiH) and the infrared stretching frequencies (νSiH) of these disilyl zinc compounds indicate that the zinc center and silyl ligand interact through a classical 2-center-2-electron bond, and the β-SiH groups do not show evidence of nonclassical interactions with the zinc center. Still, the β-SiH groups undergo β-hydrogen abstraction rather than silyl group abstraction upon reaction with the Lewis acid B(C6F5)3 to give the corresponding silylzinc hydridoborate compounds.

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