A donor-stabilized silylene 4 featuring a Ni0 -based donating ligand was synthesized. Complex 4 exhibits a pyramidalized and nucleophilic SiII center and shows a peculiar behavior due to the cooperative reactivity of Si and Ni centers. Calculations indicate that the orientation of Ni-ligands with respect to the silylene moiety is crucial in determining the role of the Ni-fragment (Lewis acid or Lewis base) towards silylene. Indeed, a simple 90° rotation of the Si-Ni bond, reverses the role of Ni, and transforms a classical silylene→Ni0 complex into an unprecedented Ni0 →silylene complex.
Keywords: Density Functional Calculations; Donor Ligands; Metallacycles; Nickel Complexes; Silylenes.
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