Olefin Metathesis Catalysis and Polymerization

Olefin metathesis is a versatile catalytic transformation in which pairs of carbon–carbon double bonds exchange substituents through metal–carbene intermediates. This reaction underpins key processes such as ring-opening metathesis polymerization (ROMP), ring-closing metathesis (RCM) and cross-metathesis (CM), each of which has shaped modern polymer synthesis and materials design. A range of transition-metal complexes—most notably ruthenium and molybdenum species bearing N-heterocyclic carbene or cyclic(alkyl)(amino)carbene ligands—balance activity, selectivity and functional-group tolerance. While Grubbs and Hoveyda–Grubbs catalysts have been central to synthetic applications, recent advances have explored latent or stimuli-responsive systems to enhance control and minimise decomposition. In polymer chemistry, ROMP affords well defined macromolecules with tunable architectures, while cross-metathesis allows post-polymerisation functionalisation and the introduction of diverse side-chain motifs. Emerging isomerization-metathesis strategies offer routes to chemical recycling of polyolefins, converting long-chain materials into valuable feedstocks such as propylene. Together, these developments underscore the global significance of metathesis catalysis in sustainable materials, fine-chemical synthesis and emerging technologies including 3D printing and biocompatible polymeric constructs.

Research from Nature Portfolio

Highly active ruthenium catalysts derived from N-vinylsulfonamide precursors have been engineered to permit low-temperature ROMP of low-strain monomers such as cyclopentene derivatives and cyclopentadiene, feedstocks conventionally resistant to polymerization due to unfavourable thermodynamics and rapid dimerization. Modulation of ligand electronics and sterics enabled controlled initiation rates from latent to ultrafast, with some catalysts exhibiting rapid propagation even at –60 °C. These systems expand the scope of accessible polymers, demonstrating continuous chain growth under mild conditions and opening avenues for the utilisation of abundant hydrocarbon feedstocks in precision polymer manufacture.

Olefin Metathesis Catalysis and Polymerization publication trend

The graph below shows the total number of articles in olefin metathesis catalysis and polymerization across all publications each year (not limited to Nature Index journals).

Technical terms

Olefin metathesis: A catalytic process exchanging alkene fragments via metal–carbene intermediates to form new carbon–carbon double bonds.

Ring-opening metathesis polymerization (ROMP): A polymerisation technique in which cyclic olefins open and link to form polymers driven by release of ring strain.

Cross-metathesis: The exchange of substituents between two different alkenes, enabling functional-group interconversion or polymer backbone modification.

Isomerization-metathesis (ISOMET): A combined reaction wherein olefin isomerization precedes or accompanies metathesis to produce targeted small-molecule products from long-chain substrates.

N-heterocyclic carbene (NHC) and cyclic(alkyl)(amino)carbene (CAAC): Strong σ-donating ligands stabilising metal centres, tuning catalytic activity, selectivity and initiation rates.

References

1. Highly active ruthenium metathesis catalysts enabling ring-opening metathesis polymerization of cyclopentadiene at low temperatures. Nature Communications (2019).
2. “Inverted” Cyclic(Alkyl)(Amino)Carbene (CAAC) Ruthenium Complex Catalyzed Isomerization Metathesis (ISOMET) of Long Chain Olefins to Propylene at Low Ethylene Pressure. Advanced Science (2024).
3. Catalytic Decomposition of Long‐Chain Olefins to Propylene via Isomerization‐Metathesis Using Latent Bicyclic (Alkyl)(Amino)Carbene‐Ruthenium Olefin Metathesis Catalysts. Angewandte Chemie International Edition (2022).
4. It is Better with Salt: Aqueous Ring-Opening Metathesis Polymerization at Neutral pH. Journal of the American Chemical Society (2020).