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Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)

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Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...

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Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
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Related Experiment Video

Updated: May 12, 2026

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization

Published on: November 29, 2018

Alcohol-promoted ring-opening alkyne metathesis polymerization.

Daniel W Paley¹, Danielle F Sedbrook, John Decatur

¹Department of Chemistry, Columbia University, 3000 Broadway, New York, NY 10027, USA.

Angewandte Chemie (International Ed. in English)

|April 10, 2013

Summary

Methanol activates an inactive molybdenum complex for ring-opening alkyne metathesis polymerization. This process is compatible with water and phenol, enabling in-situ monomer generation for advanced polymer synthesis.

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Last Updated: May 12, 2026

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization

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Published on: November 29, 2018

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes

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Published on: November 21, 2017

Area of Science:

Organometallic Chemistry
Polymer Science
Catalysis

Background:

Molybdenum alkylidyne complexes are typically inactive for polymerization.
Ring-opening alkyne metathesis polymerization (ROAMP) offers a route to novel polymer structures.
Activation methods for dormant catalysts are crucial for practical applications.

Purpose of the Study:

To activate an air-stable, dimeric molybdenum alkylidyne complex for ROAMP.
To investigate the compatibility of the activated catalyst system with various functional groups and monomer generation methods.

Main Methods:

Synthesis and characterization of a dimeric molybdenum alkylidyne complex.
Activation of the complex using methanol as a co-catalyst.
Investigation of ROAMP using various alkyne monomers, including those generated photochemically.
Compatibility studies with water and phenol-containing substrates.

Main Results:

The dimeric molybdenum alkylidyne complex was successfully activated by methanol.
The activated system efficiently catalyzed ROAMP under mild conditions.
The polymerization demonstrated excellent tolerance to water and phenol.
In-situ generation of alkyne monomers from cyclopropenones via photochemistry was compatible with the catalytic system.

Conclusions:

Methanol serves as an effective activator for a dormant molybdenum alkylidyne catalyst, enabling ROAMP.
The developed catalytic system exhibits broad functional group tolerance and compatibility with photochemical monomer generation, expanding the scope of ROAMP.
This work provides a versatile platform for synthesizing polymers with diverse structures and functionalities.