Journal Article

PUBDB-2025-03883

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Ring-Expansion Metathesis Polymerization under Confinement

Probst, P. ; Lindemann, M. ; Bruckner, J. R. ; Atwi, B. ; Wang, D. ; Fischer, F. R.Extern* ; Högler, M. ; Bauer, M.Extern* ; Hansen, N. ; Dyballa, M. ; Buchmeiser, M. R. (Corresponding author)

2025
ACS Publications Washington, DC

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Please use a persistent id in citations: doi:10.1021/jacs.4c18171

Abstract: The cationic molybdenum alkylidyne N-heterocyclic carbene (NHC) complex [Mo(C-p-OMeC6H4)(OCMe(CF3)2)2 (IMes)][B(ArF4] (IMes = 1,3-dimesitylimidazol-2-ylidene) was selectively immobilized inside the pores of ordered mesoporous silica (OMS) with pore diameters of 66, 56, and 28 Å and used in the ring-expansion metathesis polymerization (REMP) of cyclic olefins to yield cyclic polymers. A strong confinement effect was observed for cis-cyclooctene (cCOE), 1,5-cyclooctadiene (COD), (+)-2,3-endo,exo-dicarbomethoxynorborn-5-ene ((+)-DCMNBE), and 2-methyl-2-phenylcycloprop-1-ene (MPCP), allowing for the synthesis of low-molecular-weight cyclic polymers even at a high monomer concentration. The exclusive formation of cyclic polymers was demonstrated by matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry. Confinement also influences stereoselectivity, resulting in a pronounced increase in Z-selectivity and in an increased cis-syndiospecificity.

Note: ■ ACKNOWLEDGMENTSThe authors acknowledge support by the German Research Foundation (DFG) through grant numbers 358283783�SFB 1333/2 2022 and BU2174/24-1. M.H. and N.H. gratefullyacknowledge the computing time on the high-performance computer HoreKa at the NHR Center at KIT (NHR@KIT). Waiting for fulltext

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Contributing Institute(s):

1. DOOR-User (DOOR ; HAS-User)

Research Program(s):

1. 6G3 - PETRA III (DESY) (POF4-6G3) (POF4-6G3)
2. DFG project G:(GEPRIS)358283783 - SFB 1333: Molekulare heterogene Katalyse in definierten, dirigierenden Geometrien (358283783) (358283783)
3. SFB 1333 C02 - Metallkomplexe von Porphyrinoiden und Pyridylcarbenen als molekulare Photo-/Elektrokatalysatoren in definierten dirigierenden Geometrien (C02) (406663389) (406663389)

Experiment(s):

1. PETRA Beamline P65 (PETRA III)

Appears in the scientific report 2025

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