cPCET versus HAT: a direct theoretical method for distinguishing X–H bond‐activation mechanisms

JEMN Klein, G Knizia - Angewandte Chemie International …, 2018 - Wiley Online Library
Proton‐coupled electron transfer (PCET) events play a key role in countless chemical
transformations, but they come in many physical variants which are hard to distinguish …

Mechanisms for hydrogen-atom abstraction by mononuclear copper (III) cores: Hydrogen-atom transfer or concerted proton-coupled electron transfer?

M Mandal, CE Elwell, CJ Bouchey, TJ Zerk… - Journal of the …, 2019 - ACS Publications
In a possibly biomimetic fashion, formally copper (III)–oxygen complexes LCu (III)–OH (1)
and LCu (III)–OOCm (2)(L2–= N, N′-bis (2, 6-diisopropylphenyl)-2, 6 …

Radical rebound hydroxylation versus H-atom transfer in non-heme iron (III)-hydroxo complexes: reactivity and structural differentiation

MJ Drummond, CL Ford, DL Gray… - Journal of the …, 2019 - ACS Publications
The characterization of high-valent iron centers in enzymes has been aided by synthetic
model systems that mimic their reactivity or structural and spectral features. For example, the …

Spectroscopic and reactivity comparisons between nonheme oxoiron (IV) and oxoiron (V) species bearing the same ancillary ligand

V Dantignana, J Serrano-Plana… - Journal of the …, 2019 - ACS Publications
This work directly compares the spectroscopic and reactivity properties of an oxoiron (IV)
and an oxoiron (V) complex that are supported by the same neutral tetradentate N-based …

Activation of dioxygen by a mononuclear nonheme iron complex: sequential peroxo, oxo, and hydroxo intermediates

JB Gordon, AC Vilbert, IM DiMucci… - Journal of the …, 2019 - ACS Publications
The activation of dioxygen by FeII (Me3TACN)(S2SiMe2)(1) is reported. Reaction of 1 with
O2 at− 135° C in 2-MeTHF generates a thiolate-ligated (peroxo) diiron complex FeIII2 …

A Reactive, Photogenerated High-Spin (S = 2) FeIV(O) Complex via O2 Activation

JB Gordon, T Albert, A Dey, S Sabuncu… - Journal of the …, 2021 - ACS Publications
Addition of dioxygen at low temperature to the non-heme ferrous complex FeII
(Me3TACN)((OSiPh2) 2O)(1) in 2-MeTHF produces a peroxo-bridged diferric complex Fe2III …

Dioxygen-Derived Nonheme Mononuclear FeIII(OH) Complex and Its Reactivity with Carbon Radicals

V Yadav, JB Gordon, MA Siegler… - Journal of the American …, 2019 - ACS Publications
A new tetradentate, monoanionic, mixed N/O donor ligand (BNPAPh2O–) with second
coordination sphere H-bonding groups has been synthesized for stabilization of a terminal …

Iron‐Catalyzed Highly Enantioselective cis‐Dihydroxylation of Trisubstituted Alkenes with Aqueous H2O2

J Wei, L Wu, HX Wang, X Zhang… - Angewandte Chemie …, 2020 - Wiley Online Library
Reliable methods for enantioselective cis‐dihydroxylation of trisubstituted alkenes are
scarce. The iron (II) complex cis‐α‐[FeII (2‐Me2‐BQPN)(OTf) 2], which bears a tetradentate …

A Reactive Manganese (IV)–Hydroxide Complex: A Missing Intermediate in Hydrogen Atom Transfer by High-Valent Metal-Oxo Porphyrinoid Compounds

JPT Zaragoza, MA Siegler… - Journal of the American …, 2018 - ACS Publications
High-valent metal-hydroxide species are invoked as critical intermediates in both catalytic,
metal-mediated O2 activation (eg, by Fe porphyrin in Cytochrome P450) and O2 production …

Controlling the reactivity of a metal-hydroxo adduct with a hydrogen bond

AA Opalade, L Hessefort, VW Day… - Journal of the American …, 2021 - ACS Publications
The enzymes manganese lipoxygenase (MnLOX) and manganese superoxide dismutase
(MnSOD) utilize mononuclear Mn centers to effect their catalytic reactions. In the oxidized …