Ring-Expansion Metathesis Polymerization under Confinement

IF 14.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of the American Chemical Society Pub Date : 2025-02-26 DOI:10.1021/jacs.4c18171

Patrick Probst, Moritz Lindemann, Johanna R. Bruckner, Boshra Atwi, Dongren Wang, Felix R. Fischer, Marc Högler, Matthias Bauer, Niels Hansen, Michael Dyballa, Michael R. Buchmeiser

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引用次数: 0

Abstract

The cationic molybdenum alkylidyne N-heterocyclic carbene (NHC) complex [Mo(C-p-OMeC₆H₄)(OCMe(CF₃)₂)₂ (IMes)][B(Ar^F₄] (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.

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来源期刊

Journal of the American Chemical Society 化学-化学综合

CiteScore

24.40

自引率

6.00%

发文量

2398

审稿时长

1.6 months

期刊介绍： The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.