ArticleJournal of the American Chemical Society2019
Mechanism of Olefin Metathesis with Neutral and Cationic Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes.
Article in Journal of the American Chemical Society, 2019. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 10 papers.
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Who cites it
10 citing papers in PubMed.
- Tuning Regioselectivity in Cyclopolymerization through Carbene Ligand Size Modulation in Molybdenum Imido Alkylidene Catalysts.Macromolecules · 2026Article
- Applications of Olefin Metathesis in the Synthesis of Fluorinated Substrates and Design of Fluorinated Catalysts.Topics in current chemistry (Cham) · 2025Review
- Is Mn(I) More Promising Than Fe(II)-A Comparison of Mn vs Fe Complexes for Olefin Metathesis.Organometallics · 2024Article
- PyConSolv: A Python Package for Conformer Generation of (Metal-Containing) Systems in Explicit Solvent.Journal of chemical information and modeling · 2023Article
- On the Origin ofOrganometallics · 2021Article
- Olefin metathesis: what have we learned about homogeneous and heterogeneous catalysts from surface organometallic chemistry?Chemical science · 2021Review
- Cationic Group VI Metal Imido Alkylidene N-Heterocyclic Carbene Nitrile Complexes: Bench-Stable, Functional-Group-Tolerant Olefin Metathesis Catalysts.Angewandte Chemie (International ed. in English) · 2021Article
- Reversible N-Heterocyclic Carbene-Induced α-H Abstraction in Tungsten(VI) Imido Dialkyl Dialkoxide Complexes.Chemistry (Weinheim an der Bergstrasse, Germany) · 2020Article
- Origin and Use of Hydroxyl Group Tolerance in Cationic Molybdenum Imido Alkylidene N-Heterocyclic Carbene Catalysts.Angewandte Chemie (International ed. in English) · 2020Article
- Exploring the Mechanism of the Palladium-Catalyzed 3-Butene-2-ol Amination Reaction: A DFT Study.Frontiers in chemistry · 2020Article
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8 authors.
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Abstract
A series of neutral molybdenum imido alkylidene N-heterocyclic carbene (NHC) bistriflate and monotriflate monoalkoxide complexes as well as cationic molybdenum imido alkylidene triflate complexes have been subjected to NMR spectroscopic, X-ray crystallographic, and reaction kinetic measurements in order to gain a comprehensive understanding about the underlying mechanism in olefin metathesis of this new type of catalysts. On the basis of experimental evidence and on DFT calculations (BP86/def2-TZVP/D3/cosmo) for the entire mechanism, olefinic substrates coordinate trans to the NHC of neutral 16-electron complexes via an associative mechanism, followed by dissociation of an anionic ligand (e.g., triflate) and formation of an intermediary molybdacyclobutane trans to the NHC. Formation of a cationic complex is crucial in order to become olefin metathesis active. Variations in the NHC, the imido, the alkoxide, and the noncoordinating anion revealed their influence on reactivity. The reaction of neutral 16-electron complexes with 2-methoxystyrene is faster for catalysts bearing one triflate and one fluorinated alkoxide than for catalysts bearing two triflate ligands. This is also reflected by the Gibbs free energy values for the transition states, Δ G
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