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Synthesis 2025; 57(08): 1469-1474
DOI: 10.1055/a-2510-5370
DOI: 10.1055/a-2510-5370
paper
Romanian Chemists in Synthesis
Electrolyte Effect on Electrochemically Controlled Polymerizations
This work was supported by the NSF (Grant CHE-1809116 and CHE-2400314 to P.L.D., and 1532232 for NMR spectroscopy). R.N.M. was supported in part by NRT-INFEWS (Grant DGE-1735325).
Abstract
Electrochemically controlled redox-switchable polymerization uses an electric potential to bias the monomer selectivity of a catalyst. Many ferrocene-appended catalysts can exist in two oxidation states, a neutral reduced state and an oxidized cationic state. Electrochemical generation of the oxidized cationic state produces a charged species whose counteranion is determined by the identity of the supporting electrolyte anion. Herein, the role the counteranion has on monomer selectivity and polymerization kinetics is investigated. Minimal differences in monomer selectivity in the reduced state was found, however, in the oxidized state, the coordinating ability of the counteranion greatly influenced the rate of polymerization. How activity differences governed by the choice of electrolyte can be utilized to access desired diblock copolymers is also described.
Key words
redox-switchable catalysis - electrochemistry - ring-opening polymerization - organometallic chemistrySupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2510-5370.
- Supporting Information
Publication History
Received: 23 November 2024
Accepted after revision: 06 January 2025
Accepted Manuscript online:
06 January 2025
Article published online:
11 March 2025
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