Synthesis, Reactivity, and Complexation with Fe(0) of a Tight-bite Bis(N-heterocyclic silylene).

The synthesis, reactivity, and complexation with Fe(0) precursor of a tight-bite bis(N-heterocyclic silylene) (bis(NHSi)) ligand 1 are reported. The reaction of 1 with p-toluidine led to the activation of both N-H bonds across Si(II) atoms to afford a four-membered heterocyclic cyclodisilazane 2, with hydride substituents attached to five-coordinate Si atoms. A 1 : 2 reaction of 1 with Fe(CO)5 led to an intriguing dinuclear complex 3 featuring a five-membered (N-Si-Fe-Fe-Si) ring with a Fe-Fe bond distance of 2.6892(13) Å. All compounds (1-3) were thoroughly characterized by various spectroscopic methods and X-ray diffraction studies conclusively established their molecular structures. DFT calculations were carried out to shed light on bonding and energetic aspects in 1-3.

Stabilization of NH- Group Adjacent to Naked Silicon(II) Atom in Base Stabilized Aminosilylenes.

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(Nt Bu)2 ) (1 a) and Mes*NHSi(PhC(Nt 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.