ArticleInorganic chemistry2010
X-ray absorption spectroscopy and reactivity of thiolate-ligated Fe(III)-OOR complexes.
Article in Inorganic chemistry, 2010. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 7 papers.
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7 citing papers in PubMed.
- Discussing the Terms Biomimetic and Bioinspired within Bioinorganic Chemistry.Inorganic chemistry · 2024Article
- 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
- Peroxomanganese complexes as an aid to understanding redox-active manganese enzymes.Journal of biological inorganic chemistry : JBIC : a publication of the Society of Biological Inorganic Chemistry · 2014Review
- 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
- Structural and spectroscopic characterization of metastable thiolate-ligated manganese(III)-alkylperoxo species.Journal of the American Chemical Society · 2011Article
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Abstract
The reaction of a series of thiolate-ligated iron(II) complexes [Fe(II)([15]aneN(4))(SC(6)H(5))]BF(4) (1), [Fe(II)([15]aneN(4))(SC(6)H(4)-p-Cl)]BF(4) (2), and [Fe(II)([15]aneN(4))(SC(6)H(4)-p-NO(2))]BF(4) (3) with alkylhydroperoxides at low temperature (-78 °C or -40 °C) leads to the metastable alkylperoxo-iron(III) species [Fe(III)([15]aneN(4))(SC(6)H(5))(OOtBu)]BF(4) (1a), [Fe(III)([15]aneN(4))(SC(6)H(4)-p-Cl)(OOtBu)]BF(4) (2a), and [Fe(III)([15]aneN(4))(SC(6)H(4)-p-NO(2))(OOtBu)]BF(4) (3a), respectively. X-ray absorption spectroscopy (XAS) studies were conducted on the Fe(III)-OOR complexes and their iron(II) precursors. The edge energy for the iron(II) complexes (∼7118 eV) shifts to higher energy upon oxidation by ROOH, and the resulting edge energies for the Fe(III)-OOR species range from 7121-7125 eV and correlate with the nature of the thiolate donor. Extended X-ray absorption fine structure (EXAFS) analysis of the iron(II) complexes 1-3 in CH(2)Cl(2) show that their solid state structures remain intact in solution. The EXAFS data on 1a-3a confirm their proposed structures as mononuclear, 6-coordinate Fe(III)-OOR complexes with 4N and 1S donors completing the coordination sphere. The Fe-O bond distances obtained from EXAFS for 1a-3a are 1.82-1.85 Å, significantly longer than other low-spin Fe(III)-OOR complexes. The Fe-O distances correlate with the nature of the thiolate donor, in agreement with the previous trends observed for ν(Fe-O) from resonance Raman (RR) spectroscopy, and supported by optimized geometries obtained from density functional theory (DFT) calculations. Reactivity and kinetic studies on 1a- 3a show an important influence of the thiolate donor.
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