Water-Accelerated Decomposition of Olefin Metathesis Catalysts
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In this article , the authors 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.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.read more
Citations
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Rapid Aerial Oxidation of Ruthenium-Dithiocatecholate Catalysts: A Challenge to Stereoretentive Olefin Metathesis
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Mesomeric Acceleration Counters Slow Initiation of Ruthenium–CAAC Catalysts for Olefin Metathesis (CAAC = Cyclic (Alkyl)(Amino) Carbene)
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References
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Journal ArticleDOI
Mechanism and Activity of Ruthenium Olefin Metathesis Catalysts
TL;DR: The origins of the observed substituent effects as well as the implications of these studies for the design and implementation of new olefin metathesis catalysts and substrates are discussed in detail.
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Olefin metathesis and metathesis polymerization
Kenneth J. Ivin,I. C Mol +1 more
TL;DR: The metal carbene/metallacyclobutane mechanism has been studied extensively in the literature as mentioned in this paper, with a focus on the use of a ring-opening metathesis.
Journal ArticleDOI
Recent developments in ruthenium anticancer drugs.
TL;DR: A diversity of modes of action of Ru anticancer drugs is likely to enhance their anticancer activities and to reduce the potential for them to develop tumour resistance.
Journal ArticleDOI
Isolated Seven-Coordinate Ru(IV) Dimer Complex with [HOHOH]− Bridging Ligand as an Intermediate for Catalytic Water Oxidation
TL;DR: A seven-coordinate Ru(IV) dimer complex containing a [HOHOH](-) bridging ligand that has a short O...O distance and is hydrogen bonded to two water molecules may contribute to a deeper understanding of the mechanism for catalytic water oxidation.