Aminosilylene, comprising reactive NH- and Si(II) sites next to each other, is an intriguing class of compounds due to its ability to show diverse reactivity. However, stabilizing the reactive NH- group next to the free Si(II) atom is challenging and has not yet been achieved. Herein, we report the first examples of base stabilized free aminosilylenes Ar*NHSi(PhC(N^t Bu)₂ ) (1 a) and Mes*NHSi(PhC(N^t Bu)₂ ) (1 b) (Ar*=2,6-dibenzhydryl-4-methylphenyl and Mes*=2,4,6-tri-tert-butylphenyl), tolerating a NH- group next to the naked Si(II) atom. Remarkably, 1 a and 1 b exhibited interesting differences in their reactivity upon heating. With 1 a, an intramolecular C(sp³ )-H activation of one of the benzhydryl methine hydrogen atoms to the Si(II) atom produced the five-membered cyclic silazane 2. However, with 1 b, a rare 1,2-hydrogen shift to the Si(II) atom afforded a silanimine 3, with a hydride ligand attached to an unsaturated silicon atom. Further, the coordination capabilities of 1 a were also tested with Ru(II) and Fe(0) precursors. Treatments of 1 a with [Ru(η⁶ -p-cymene)Cl₂ ]₂ led to the isolation of a η⁶ -arene tethered complex [RuCl₂ {Ar*NHSi(PhC(^t BuN)₂ )-κ¹ -Si-η⁶ -arene}] (4), whereas with the Fe(CO)₅ precursor a Fe(0) complex [Fe(CO)₄ {Ar*NHSi(PhC(^t BuN)₂ )-κ¹ -Si}] (5) was obtained. Density functional theory (DFT) calculations were conducted to shed light on the structural, bonding, and energetic aspects in 1-5.

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