ArticleJournal of the American Chemical Society2014
Carboxylate-assisted C(sp³)-H activation in olefin metathesis-relevant ruthenium complexes.
Article in Journal of the American Chemical Society, 2014. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 11 papers.
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Who cites it
11 citing papers in PubMed.
- Construction of quaternary stereocenters via Ru-catalyzed asymmetric ring-closing metathesis.Nature communications · 2026Article
- An Anthracene-Thiolate-Ligated Ruthenium Complex: Computational Insights into Z-Stereoselective Cross Metathesis.The journal of physical chemistry. A · 2023Article
- Ru-catalysed oxidative cyclisation of 1,5-dienes: an unprecedented role for the co-oxidant.RSC advances · 2020Article
- Recent advances in ruthenium-based olefin metathesis.Chemical Society reviews · 2018Review
- Substrate-Selective C-H Functionalization for the Preparation of Organosulfur Compounds from Crude Oil-Derived Components.ACS omega · 2017Article
- Cationic ruthenium alkylidene catalysts bearing phosphine ligands.Dalton transactions (Cambridge, England : 2003) · 2016Article
- Mechanistic insights into cobalt(ii/iii)-catalyzed C-H oxidation: a combined theoretical and experimental study.Chemical science · 2015Article
- Tuning the Reactivity of Radical through a Triplet Diradical Cu(II) Intermediate in Radical Oxidative Cross-Coupling.Scientific reports · 2015Article
- Carboxylate-assisted C-H activation of phenylpyridines with copper, palladium and ruthenium: a mass spectrometry and DFT study.Chemical science · 2015Article
- Ruthenium-Catalyzed Asymmetric Hydrohydroxyalkylation of Butadiene: The Role of the Formyl Hydrogen Bond in Stereochemical Control.Journal of the American Chemical Society · 2015Article
- Ru-BasedChemical science · 2014Article
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Authors and funding
7 authors.
Funding
Abstract
The mechanism of C-H activation at metathesis-relevant ruthenium(II) benzylidene complexes was studied both experimentally and computationally. Synthesis of a ruthenium dicarboxylate at a low temperature allowed for direct observation of the C-H activation step, independent of the initial anionic ligand-exchange reactions. A first-order reaction supports an intramolecular concerted metalation-deprotonation mechanism with ΔG(‡)(298K) = 22.2 ± 0.1 kcal·mol(-1) for the parent N-adamantyl-N'-mesityl complex. An experimentally determined ΔS(‡) = -5.2 ± 2.6 eu supports a highly ordered transition state for carboxylate-assisted C(sp(3))-H activation. Experimental results, including measurement of a large primary kinetic isotope effect (k(H)/k(D) = 8.1 ± 1.7), agree closely with a computed six-membered carboxylate-assisted C-H activation mechanism where the deprotonating carboxylate adopts a pseudo-apical geometry, displacing the aryl ether chelate. The rate of cyclometalation was found to be influenced by both the electronics of the assisting carboxylate and the ruthenium ligand environment.
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