A silyliumylidene ion 2 stabilized by two σ-donating Ni(0)- and Pd(0)-fragments was successfully synthesized. Due to the σ-donation of M→Si interactions, 2 presents a pyramidalized cationic silicon center with a localized lone pair. The additional coordination of basic Pd(0) fragment to the mono-Ni(0)-stabilized silyliumylidene 1 results in a higher HOMO level and an unchanged HOMO-LUMO gap and thus, 2 remains highly reactive. Interestingly, the coordination mode at the Si center is closely related to the nature of M-ligands. Indeed, the donor/donor-stabilized silyliumylidene ion 2 has been transformed into a donor/acceptor-stabilized ion 13, featuring a trigonal planar Si center with a vacant orbital, just via a ligand exchange reaction from PCy/NHC toward PMe.
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Silyliumylidene Ion Stabilized by Two σ-Donating Ni(0)- and Pd(0)-Fragments.
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Laboratoire Hétérochimie Fondamentale et Appliquée (UMR 5069), Université de Toulouse, CNRS, 118 route de Narbonne, F-31062, Toulouse, France.
A silyliumylidene ion 2 stabilized by two σ-donating Ni(0)- and Pd(0)-fragments was successfully synthesized. Due to the σ-donation of M→Si interactions, 2 presents a pyramidalized cationic silicon center with a localized lone pair. The additional coordination of basic Pd(0) fragment to the mono-Ni(0)-stabilized silyliumylidene 1 results in a higher HOMO level and an unchanged HOMO-LUMO gap and thus, 2 remains highly reactive.
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Department of Chemistry, WACKER-Institute of Silicon Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, 85748 Garching bei München, Germany.
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