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Updated: Jun 25, 2025
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Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
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Silyliumylidene Ion Stabilized by Two σ-Donating Ni(0)- and Pd(0)-Fragments
Shintaro Takahashi1, Yugo Kazama2, Norio Nakata2
1Laboratoire Hétérochimie Fondamentale et Appliquée (UMR 5069), Université de Toulouse, CNRS, 118 route de Narbonne, F-31062, Toulouse, France.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|May 23, 2024
Summary
A novel silyliumylidene ion stabilized by nickel and palladium fragments was synthesized. Ligand exchange altered its structure, demonstrating tunable reactivity in organosilicon chemistry.
Area of Science:
- Organometallic Chemistry
- Silicon Chemistry
- Coordination Chemistry
Background:
- Silyliumylidene ions are highly reactive silicon species.
- Stabilization of silyliumylidenes is crucial for their study and application.
- Metal-ligand interactions significantly influence electronic properties.
Purpose of the Study:
- To synthesize and characterize a novel silyliumylidene ion stabilized by Ni(0) and Pd(0) fragments.
- To investigate the effect of σ-donation from metal fragments on the silicon center's geometry and reactivity.
- To explore the transformation of donor/donor-stabilized silyliumylidenes to donor/acceptor-stabilized species via ligand exchange.
Main Methods:
- Synthesis of a silyliumylidene ion featuring two σ-donating Ni(0) and Pd(0) fragments.
- Spectroscopic and structural analysis to determine the electronic and geometric properties.
- Ligand exchange reactions to modify the stabilization environment of the silicon center.
Main Results:
- Successful synthesis of a silyliumylidene ion (2) with a pyramidalized cationic silicon center due to M→Si σ-donation.
- Enhanced reactivity of silyliumylidene ion 2 due to a higher HOMO level.
- Transformation of the donor/donor-stabilized silyliumylidene ion 2 into a donor/acceptor-stabilized ion (13) with a trigonal planar silicon center via ligand exchange.
Conclusions:
- The σ-donation from Ni(0) and Pd(0) fragments effectively stabilizes the silyliumylidene ion.
- The coordination mode at the silicon center is tunable by altering the nature of the M-ligands.
- Ligand exchange offers a pathway to modify the electronic structure and coordination geometry of silyliumylidene ions.
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