ArticleJournal of the American Chemical Society2010
Influence of the nitrogen donors on nonheme iron models of superoxide reductase: high-spin Fe(III)-OOR complexes.
Article in Journal of the American Chemical Society, 2010. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 20 papers.
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Who cites it
20 citing papers in PubMed.
- Review
- Mechanistic Insights into the Reductive N-O Bond Cleavage ofACS organic & inorganic Au · 2025Article
- Discussing the Terms Biomimetic and Bioinspired within Bioinorganic Chemistry.Inorganic chemistry · 2024Article
- A high-spin alkylperoxo-iron(iii) complex withChemical science · 2024Article
- A Combined Spectroscopic and Computational Study on the Mechanism of Iron-Catalyzed Aminofunctionalization of Olefins Using Hydroxylamine Derived N-O Reagent as the "Amino" Source and "Oxidant".Journal of the American Chemical Society · 2022Article
- Proton-Coupled Electron Transfer in Organic Synthesis: Fundamentals, Applications, and Opportunities.Topics in current chemistry (Cham) · 2016Review
- Perturbing the Copper(III)-Hydroxide Unit through Ligand Structural Variation.Journal of the American Chemical Society · 2016Article
- Thioether-ligated iron(II) and iron(III)-hydroperoxo/alkylperoxo complexes with an H-bond donor in the second coordination sphere.Dalton transactions (Cambridge, England : 2003) · 2014Article
- Secondary coordination sphere influence on the reactivity of nonheme iron(II) complexes: an experimental and DFT approach.Journal of the American Chemical Society · 2013Article
- Correlation between structural, spectroscopic, and reactivity properties within a series of structurally analogous metastable manganese(III)-alkylperoxo complexes.Journal of the American Chemical Society · 2013Article
- Antioxidant capacity of two novel bioactive Fe(III)-cyclophane complexes.Molecules (Basel, Switzerland) · 2013Article
- Characterization of a thiolato iron(III) Peroxy dianion complex.Angewandte Chemie (International ed. in English) · 2012Article
- Axial and equatorial ligand effects on biomimetic cysteine dioxygenase model complexes.Organic & biomolecular chemistry · 2012Article
- Preparation of aluminum(III) (bis(amido)pyridine)(thiolate) complexes: unexpected transmetalation mediated by LiAlH(4).Inorganica chimica acta · 2012Article
- Preparation and properties of a monomeric high-spin Mn(V)-oxo complex.Journal of the American Chemical Society · 2012Article
- Mechanism of S-oxygenation by a cysteine dioxygenase model complex.The journal of physical chemistry. A · 2012Article
- Structural and spectroscopic characterization of metastable thiolate-ligated manganese(III)-alkylperoxo species.Journal of the American Chemical Society · 2011Article
- Spectroscopic and computational characterization of CuII-OOR (R = H or cumyl) complexes bearing a Me6-tren ligand.Dalton transactions (Cambridge, England : 2003) · 2011Article
- X-ray absorption spectroscopy and reactivity of thiolate-ligated Fe(III)-OOR complexes.Inorganic chemistry · 2010Article
- Density Functional Theory Calculations on Fe-O and O-O Cleavage of Ferric Hydroperoxide Species: Role of axial ligand and spin state.Inorganica chimica acta · 2010Article
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Abstract
A new five-coordinate, (N(4)S(thiolate))Fe(II) complex, containing tertiary amine donors, [Fe(II)(Me(4)[15]aneN(4))(SPh)]BPh(4) (2), was synthesized and structurally characterized as a model of the reduced active site of superoxide reductase (SOR). Reaction of 2 with tert-butyl hydroperoxide (tBuOOH) at -78 degrees C led to the generation of the alkylperoxo-iron(III) complex [Fe(III)(Me(4)[15]aneN(4))(SPh)(OOtBu)](+) (2a). The nonthiolate-ligated complex, [Fe(II)(Me(4)[15]aneN(4))(OTf)(2)] (3), was also reacted with tBuOOH and yielded the corresponding alkylperoxo complex [Fe(III)(Me(4)[15]aneN(4))(OTf)(OOtBu)](+) (3a) at an elevated temperature of -23 degrees C. These species were characterized by low-temperature UV-vis, EPR, and resonance Raman spectroscopies. Complexes 2a and 3a exhibit distinctly different spectroscopic signatures than the analogous alkylperoxo complexes [Fe(III)([15]aneN(4))(SAr)(OOR)](+), which contain secondary amine donors. Importantly, alkylation at nitrogen leads to a change from low-spin (S = 1/2) to high-spin (S = 5/2) of the iron(III) center. The resonance Raman data reveal that this change in spin state has a large effect on the nu(Fe-O) and nu(O-O) vibrations, and a comparison between 2a and the nonthiolate-ligated complex 3a shows that axial ligation has an additional significant impact on these vibrations. To our knowledge this study is the first in which the influence of a ligand trans to a peroxo moiety has been evaluated for a structurally equivalent pair of high-spin/low-spin peroxo-iron(III) complexes. The implications of spin state and thiolate ligation are discussed with regard to the functioning of SOR.
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