Monomer-Dependent Selectivity in Sulfur-Containing Ring-Opening Copolymerisation : Bimetallic Catalysis for Predictive Design of Degradable Polymers

DOI zum Zitieren der Version auf EPub Bayreuth: https://doi.org/10.15495/EPub_UBT_00009055
URN to cite this document: urn:nbn:de:bvb:703-epub-9055-0

Title data

Rampura Manjunatha, Bhargav ; Sengoden, Mani ; Stühler, Merlin R. ; Langer, Robert ; Darensbourg, Donald J. ; Plajer, Alex:
Monomer-Dependent Selectivity in Sulfur-Containing Ring-Opening Copolymerisation : Bimetallic Catalysis for Predictive Design of Degradable Polymers.
In: Angewandte Chemie International Edition. Vol. 64 (2025) Issue 42 . - e202508985.
ISSN 1521-3773
DOI der Verlagsversion: https://doi.org/10.1002/anie.202508985

	Format: PDF Name: Angew Chem Int Ed - 2025 - Manjunatha - Monomer‐Dependent Selectivity in Sulfur‐Containing Ring‐Opening Copolymerisation .pdf Version: Published Version Available under License Creative Commons BY 4.0: Attribution
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Project information

Project title:	Project's official title Project's id Kooperative Abfallverwertung: Präzisionspolymere aus Kohlenstoffdioxid und elementarem Schwefel 542928411 Open Access Publizieren No information
Project financing:	Deutsche Forschungsgemeinschaft

Abstract

Sulfur-containing polymers offer unique opportunities for advanced materials due to their inherent degradability, high refractive indices, and potential for chemical recyclability. Yet, synthetic strategies for their precise construction remain underdeveloped and monomer selection rules to achieve this are elusive. Herein, we achieve the first comprehensive evaluation of sulfurated ring-opening copolymerisations (ROCOP) performed under unified conditions using a single heterobimetallic Cr(III)/Rb(I) catalyst platform. Although such catalysts are largely unexplored in sulfur-based ROCOP, our study demonstrates their remarkable synergistic performance in controlling both activity and selectivity across diverse heteroallene/epoxide systems. We identify carbonyl sulfide (COS) as the most promising monomer, enabling perfectly alternating copolymers under mild conditions on kinetic grounds. As a close second, PhNCS emerges as a viable, easier to handle, alternative that offers selective access to sulfur-containing copolymers. In contrast, thioanhydrides and CS2 show progressively lower selectivity, with increasing O/S scrambling and small molecule byproduct formation. This study provides the first predictive framework linking sulfur monomer identity to selectivity and reactivity under unified conditions, enabling rational design of degradable sulfur-rich polymers.

Further data

Item Type:	Article in a journal
Keywords:	Bimetallic catalysis; Ring opening copolymerisation; Sulfur-containing polymers
DDC Subjects:	500 Science > 540 Chemistry
Institutions of the University:	Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Junior Professor Polymers for Electrooptical and Sensory Applications > Junior Professor Polymers for Electrooptical and Sensory Applications - Juniorprof. Dr. Alex Johannes Plajer Research Institutions > Affiliated Institutes > Bavarian Polymer Institute (BPI) Faculties Faculties > Faculty of Biology, Chemistry and Earth Sciences Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Junior Professor Polymers for Electrooptical and Sensory Applications Research Institutions Research Institutions > Affiliated Institutes
Language:	English
Originates at UBT:	Yes
URN:	urn:nbn:de:bvb:703-epub-9055-0
Date Deposited:	31 Mar 2026 10:23
Last Modified:	31 Mar 2026 10:23
URI:	https://epub.uni-bayreuth.de/id/eprint/9055

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