Dioxygen binding to complexes with FeII2(μOH) 2 cores

Steric control of activation barriers and O 2-adduct formation

Sergey V. Kryatov, Sonia Taktak, Ivan V. Korendovych, Elena V. Rybak-Akimova, J. Kaizer, Stéphane Torelli, Xiaopeng Shan, Sanjay Mandal, Vicki L. MacMurdo, Antoni Mairata I Payeras, Lawrence Que

Research output: Contribution to journalArticle

68 Citations (Scopus)

Abstract

A series of complexes with [FeII2(μ-OH) 2] cores has been synthesized with N3 and N4 ligands and structurally characterized to serve as models for nonheme diiron(II) sites in enzymes that bind and activate O2. These complexes react with O2 in solution via bimolecular rate-limiting steps that differ in rate by 10 3-fold, depending on ligand denticity and steric hindrance near the diiron center. Low-temperature trapping of a (μ-oxo)(μ-1,2-peroxo) diiron(III) intermediate after O2 binding requires sufficient steric hindrance around the diiron center and the loss of a proton (presumably that of a hydroxo bridge or a yet unobserved hydroperoxo intermediate). The relative stability of these and other (μ-1,2-peroxo)diiron(III) intermediates suggests that these species may not be on the direct pathway for dioxygen activation.

Original languageEnglish
Pages (from-to)85-99
Number of pages15
JournalInorganic Chemistry
Volume44
Issue number1
DOIs
Publication statusPublished - Jan 10 2005

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adducts
Chemical activation
activation
Oxygen
Ligands
ligands
Protons
enzymes
trapping
protons
Enzymes
Temperature

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Dioxygen binding to complexes with FeII2(μOH) 2 cores : Steric control of activation barriers and O 2-adduct formation. / Kryatov, Sergey V.; Taktak, Sonia; Korendovych, Ivan V.; Rybak-Akimova, Elena V.; Kaizer, J.; Torelli, Stéphane; Shan, Xiaopeng; Mandal, Sanjay; MacMurdo, Vicki L.; Mairata I Payeras, Antoni; Que, Lawrence.

In: Inorganic Chemistry, Vol. 44, No. 1, 10.01.2005, p. 85-99.

Research output: Contribution to journalArticle

Kryatov, SV, Taktak, S, Korendovych, IV, Rybak-Akimova, EV, Kaizer, J, Torelli, S, Shan, X, Mandal, S, MacMurdo, VL, Mairata I Payeras, A & Que, L 2005, 'Dioxygen binding to complexes with FeII2(μOH) 2 cores: Steric control of activation barriers and O 2-adduct formation', Inorganic Chemistry, vol. 44, no. 1, pp. 85-99. https://doi.org/10.1021/ic0485312
Kryatov, Sergey V. ; Taktak, Sonia ; Korendovych, Ivan V. ; Rybak-Akimova, Elena V. ; Kaizer, J. ; Torelli, Stéphane ; Shan, Xiaopeng ; Mandal, Sanjay ; MacMurdo, Vicki L. ; Mairata I Payeras, Antoni ; Que, Lawrence. / Dioxygen binding to complexes with FeII2(μOH) 2 cores : Steric control of activation barriers and O 2-adduct formation. In: Inorganic Chemistry. 2005 ; Vol. 44, No. 1. pp. 85-99.
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