Water-Accelerated Decomposition of Olefin Metathesis Catalysts
Journal article, Peer reviewed
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Date
2023Metadata
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- Department of Chemistry [459]
- Registrations from Cristin [10863]
Abstract
Water is ubiquitous in olefin metathesis, at levels ranging from contaminant to cosolvent. It is also non-benign. Water-promoted catalyst decomposition competes with metathesis, even for “robust” ruthenium catalysts. Metathesis is hence typically noncatalytic for demanding reactions in water-rich environments (e.g., chemical biology), a challenge as the Ru decomposition products promote unwanted reactions such as DNA degradation. To date, only the first step of the decomposition cascade is understood: catalyst aquation. Here we demonstrate that the aqua species dramatically accelerate both β-elimination of the metallacyclobutane intermediate and bimolecular decomposition of four-coordinate [RuCl(H2O)n(L)(═CHR)]Cl. Decomposition can be inhibited by blocking aquation and β-elimination.