ArticleChemical communications (Cambridge, England)2023
Variable temperature kinetic isotope effects demonstrate extensive tunnelling in the C-H activation reactivity of a transition metal-oxo complex.
Article in Chemical communications (Cambridge, England), 2023. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 8 papers.
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Who cites it
8 citing papers in PubMed, 19 citations in OpenAlex.
- Evidence for Site-Specific Tunneling in H Atom Uptake at the Surface of Polyoxovanadate-Alkoxides.JACS Au · 2026Article
- Article
- Impact of Structural Flexibility on Tunneling Contribution to the Reaction Mechanism of Spontaneous Succinimide Formation in Asn-Gly-Containing Peptides.Biomolecules · 2026Article
- Mechanistic Continuum from Stepwise to Concerted Proton-Coupled Electron Transfer Pathways at a Synthetic Tricopper Cluster.Journal of the American Chemical Society · 2026Article
- Thermodynamic Principles Behind Mechanisms and Reactivities: Hydrogen Atom Abstraction and Related Radical Reactions.Accounts of chemical research · 2026Article
- Consistent and Generalizable Effective Model Hamiltonian Framework for Studying Nonadiabatic Dynamics in the Condensed Phase.Journal of chemical theory and computation · 2025Review
- C(spJournal of the American Chemical Society · 2025Article
- Reconciling Imbalanced and Nonadiabatic Reactivity in Transition Metal-Oxo-Mediated Concerted Proton Electron Transfer (CPET).The journal of physical chemistry letters · 2023Article
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Authors and funding
3 authors at 2 institutions in 1 country.
Funding
Abstract
There has been recent interest about how the rates of concerted proton electron transfer (CPET) are affected by the thermodynamic parameters of intermediates from stepwise PT or ET reactions. Semiclassical arguments have been used to explain these trends despite the importance of quantum mechanical tunneling in CPET reactions. Here we report variable temperature kinetic isotope effect (KIE) data for the reactivity of a terminal Co-oxo complex with C-H bonds. The KIEs for the oxidation of both 9,10-dihydroanthracene (DHA) and fluorene have significant tunneling contributions and fluorene has a largely temperature-insensitive KIE which is inconsistent with semiclassical models. These findings support recent calls for a more detailed understanding of tunneling effects in thermodynamically imbalanced CPET reactions.
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