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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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When a Side Reaction Is a Benefit: A Catalyst-Free Route to Obtain High-Molecular Cobaltocenium-Functionalized
Anastasia N Kocheva1, Konstantin V Deriabin1, Igor Perevyazko2
1Institute of Chemistry, St. Petersburg State University, 7/9 Universitetskaya Nab., 199034 St. Petersburg, Russia.
Polymers
|October 26, 2024
Summary
New cobaltocenium-containing polysiloxanes (Cc-PDMSs) were synthesized and exhibit significant molecular weight increase and gelation. These redox-active polymers show promise for electronic applications and energy storage devices.
Area of Science:
- Organometallic Chemistry
- Polymer Science
- Materials Science
Background:
- Development of functional polymers for advanced applications.
- Need for redox-active materials in electronics and energy storage.
- Cobaltocenium complexes offer unique electrochemical properties.
Purpose of the Study:
- To synthesize novel cobaltocenium-containing polysiloxanes (Cc-PDMSs).
- To investigate the gelation behavior and redox properties of Cc-PDMSs.
- To explore their potential in electronic applications and energy storage.
Main Methods:
- Catalyst-free hydroamination reaction between ethynylcobaltocenium hexafluorophosphate and amino-functionalized polysiloxanes.
- Characterization using various spectroscopic techniques (NMR, IR, UV-Vis, XPS).
- Electrochemical analysis via cyclic voltammetry.
Main Results:
- Successful synthesis of Cc-PDMSs with high conversion of amino groups (85%).
- Observed significant 'gelation' and molecular weight increase (approx. 30 times) upon storage.
- Demonstrated redox activity (CoII/CoIII transitions) and solubility of gelated Cc-PDMSs.
Conclusions:
- The synthetic strategy effectively increases molecular weight and introduces cobaltocenium groups.
- The resulting Cc-PDMSs exhibit tunable redox properties and enhanced film-forming capabilities.
- Potential applications include modified electrodes, electrochromic devices, and battery components.
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