Metal–Free Ring–Opening Metathesis Polymerization with Hydrazonium Initiators

18 January 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


A new strategy for the ring–opening metathesis polymerization (ROMP) of cycloalkenes 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 (Mn ≤ 9.4 kg/mol) with relatively low dispersities (Đ ≤ 1.4). The optimized conditions showed efficiency comparable to that achieved with Grubbs’ catalyst. A positive correlation between monomer to initiator ratio and degree of polymerization was revealed through NMR spectroscopy.


Ring-opening metathesis polymerization
carbonyl-olefin metathesis
olefin metathesis

Supplementary materials

Supporting Information
Experimental details, characterization data, spectra and traces, and computational details.


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