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Metal‐Free Ring‐Opening Metathesis Polymerization with Hydrazonium Initiators**

Phong K. Quach, Jesse H. Hsu, Ivan Keresztes, Brett P. Fors, Tristan H. Lambert

2022Angewandte Chemie International Edition27 citationsDOIOpen Access PDF

Abstract

Abstract The ring‐opening metathesis polymerization (ROMP) of cyclopropenes using hydrazonium initiators is described. The initiators, which are formed by the condensation of 2,3‐diazabicyclo[2.2.2]octane and an aldehyde, polymerize cyclopropene monomers by a sequence of [3+2] cycloaddition and cycloreversion reactions. This process generates short chain polyolefins ( M n ≤9.4 kg mol −1 ) with relatively low dispersities ( Đ ≤1.4). The optimized conditions showed efficiency comparable to that achieved with Grubbs’ 2 nd generation catalyst for the polymerization of 3‐methyl‐3‐phenylcyclopropene. A positive correlation between monomer to initiator ratio and degree of polymerization was revealed through NMR spectroscopy.

Topics & Concepts

PolymerizationROMPMetathesisPolymer chemistryMonomerRing-opening metathesis polymerisationChemistryRing-opening polymerizationChain-growth polymerizationOctaneRadical polymerizationOrganic chemistryPolymerSynthetic Organic Chemistry MethodsChemical Synthesis and AnalysisOrganometallic Complex Synthesis and Catalysis