ArticleJournal of the American Chemical Society2013
Comparison of high-spin and low-spin nonheme Fe(III)-OOH complexes in O-O bond homolysis and H-atom abstraction reactivities.
Article in Journal of the American Chemical Society, 2013. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 27 papers.
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Who cites it
27 citing papers in PubMed.
- High-Valent Late Transition Metal-Oxo Complexes: Breaking Boundaries at the Oxo Wall and Beyond.Chemical reviews · 2026Review
- Review
- Generation of [(N4Py)Fe(IV)═O]Inorganic chemistry · 2025Article
- Substrate-Specific Coupling of OACS catalysis · 2022Article
- Antisymmetric Spin Exchange in a μ-1,2-Peroxodicopper(II) Complex with an Orthogonal Cu-O-O-Cu Arrangement andJACS Au · 2022Article
- The Apparently Unreactive Substrate Facilitates the Electron Transfer for Dioxygen Activation in Rieske Dioxygenases.Chemistry (Weinheim an der Bergstrasse, Germany) · 2022Article
- Second-sphere effects on HChemical science · 2021Article
- Mechanistic insights into dioxygen activation by a manganese corrole complex: a broken-symmetry DFT study.RSC advances · 2021Article
- ScJournal of the American Chemical Society · 2020Article
- How Metal Ion Lewis Acidity and Steric Properties Influence the Barrier to Dioxygen Binding, Peroxo O-O Bond Cleavage, and Reactivity.Journal of the American Chemical Society · 2019Article
- A catalytic antioxidant for limiting amyloid-beta peptide aggregation and reactive oxygen species generation.Chemical science · 2019Article
- HACS catalysis · 2018Article
- NRVS Studies of the Peroxide Shunt Intermediate in a Rieske Dioxygenase and Its Relation to the Native FeJournal of the American Chemical Society · 2018Article
- A structurally-characterized peroxomanganese(iv) porphyrin from reversible OChemical science · 2018Article
- Dioxygen Activation and O-O Bond Formation Reactions by Manganese Corroles.Journal of the American Chemical Society · 2017Article
- Peroxide Activation for Electrophilic Reactivity by the Binuclear Non-heme Iron Enzyme AurF.Journal of the American Chemical Society · 2017Article
- Reactivity of a Cobalt(III)-Hydroperoxo Complex in Electrophilic Reactions.Inorganic chemistry · 2016Article
- Nuclear Resonance Vibrational Spectroscopic Definition of Peroxy Intermediates in Nonheme Iron Sites.Journal of the American Chemical Society · 2016Article
- Mono- and binuclear non-heme iron chemistry from a theoretical perspective.Journal of biological inorganic chemistry : JBIC : a publication of the Society of Biological Inorganic Chemistry · 2016Review
- Rate-Determining Attack on Substrate Precedes Rieske Cluster Oxidation during Cis-Dihydroxylation by Benzoate Dioxygenase.Biochemistry · 2015Article
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5 authors.
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Abstract
The geometric and electronic structures and reactivity of an S = 5/2 (HS) mononuclear nonheme (TMC)Fe(III)-OOH complex are studied by spectroscopies, calculations, and kinetics and compared with the results of previous studies of S = 1/2 (LS) Fe(III)-OOH complexes to understand parallels and differences in mechanisms of O-O bond homolysis and electrophilic H-atom abstraction reactions. The homolysis reaction of the HS [(TMC)Fe(III)-OOH](2+) complex is found to involve axial ligand coordination and a crossing to the LS surface for O-O bond homolysis. Both HS and LS Fe(III)-OOH complexes are found to perform direct H-atom abstraction reactions but with very different reaction coordinates. For the LS Fe(III)-OOH, the transition state is late in O-O and early in C-H coordinates. However, for the HS Fe(III)-OOH, the transition state is early in O-O and further along in the C-H coordinate. In addition, there is a significant amount of electron transfer from the substrate to the HS Fe(III)-OOH at transition state, but that does not occur in the LS transition state. Thus, in contrast to the behavior of LS Fe(III)-OOH, the H-atom abstraction reactivity of HS Fe(III)-OOH is found to be highly dependent on both the ionization potential and the C-H bond strength of the substrate. LS Fe(III)-OOH is found to be more effective in H-atom abstraction for strong C-H bonds, while the higher reduction potential of HS Fe(III)-OOH allows it to be active in electrophilic reactions without the requirement of O-O bond cleavage. This is relevant to the Rieske dioxygenases, which are proposed to use a HS Fe(III)-OOH to catalyze cis-dihydroxylation of a wide range of aromatic compounds.
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