Unknown

Dataset Information

0

Characterization and reactivity study of non-heme high-valent iron-hydroxo complexes.

ABSTRACT: A terminal FeIIIOH complex, [FeIII(L)(OH)]2- (1), has been synthesized and structurally characterized (H4L = 1,2-bis(2-hydroxy-2-methylpropanamido)benzene). The oxidation reaction of 1 with one equiv. of tris(4-bromophenyl)ammoniumyl hexachloroantimonate (TBAH) or ceric ammonium nitrate (CAN) in acetonitrile at -45 °C results in the formation of a FeIIIOH ligand radical complex, [FeIII(L˙)(OH)]- (2), which is hereby characterized by UV-visible, 1H nuclear magnetic resonance, electron paramagnetic resonance, and X-ray absorption spectroscopy techniques. The reaction of 2 with a triphenylcarbon radical further gives triphenylmethanol and mimics the so-called oxygen rebound step of Cpd II of cytochrome P450. Furthermore, the reaction of 2 was explored with different 4-substituted-2,6-di-tert-butylphenols. Based on kinetic analysis, a hydrogen atom transfer (HAT) mechanism has been established. A pK a value of 19.3 and a BDFE value of 78.2 kcal/mol have been estimated for complex 2.

SUBMITTER: Keshari K 

PROVIDER: S-EPMC8179568 | biostudies-literature | 2021 Jan

REPOSITORIES: biostudies-literature

Json Xml
altmetric image

Publications

Characterization and reactivity study of non-heme high-valent iron-hydroxo complexes.

Keshari Kritika K   Bera Moumita M   Velasco Lucía L   Munshi Sandip S   Gupta Geetika G   Moonshiram Dooshaye D   Paria Sayantan S  

Chemical science 20210127 12

A terminal Fe<sup>III</sup>OH complex, [Fe<sup>III</sup>(L)(OH)]<sup>2-</sup> (<b>1</b>), has been synthesized and structurally characterized (H<sub>4</sub>L = 1,2-bis(2-hydroxy-2-methylpropanamido)benzene). The oxidation reaction of <b>1</b> with one equiv. of <i>tris</i>(4-bromophenyl)ammoniumyl hexachloroantimonate (TBAH) or ceric ammonium nitrate (CAN) in acetonitrile at -45 °C results in the formation of a Fe<sup>III</sup>OH ligand radical complex, [Fe<sup>III</sup>(L˙)(OH)]<sup>-</sup> (<b  ...[more]

Similar Datasets

Unknown Exploring the Limits of Dative Boratrane Bonding: Iron as a Strong Lewis Base in Low-Valent Non-Heme Iron-Nitrosyl Complexes.
| S-EPMC7640944 | biostudies-literature
Unknown Reactivity Properties of Mixed- and High-Valent Bis(μ-Hydroxide)-Dinickel Complexes.
| S-EPMC8554787 | biostudies-literature
Unknown Thermodynamic and Kinetic Studies of Mononuclear Non-Heme High-Valent (FeO)&lt;sup&gt;2+&lt;/sup&gt; Complexes.
| S-EPMC11800002 | biostudies-literature
Unknown Electrostatically regulated active site assembly governs reactivity in non-heme iron halogenases.
| S-EPMC10245910 | biostudies-literature
Unknown Intramolecular Hydrogen-Bond Interactions Tune Reactivity in Biomimetic Bis(μ-hydroxo)dicobalt Complexes.
| S-EPMC10294290 | biostudies-literature
Unknown Intense Photoinduced Intervalence Charge Transfer in High-Valent Iron Mixed Phenolate/Carbene Complexes.
| S-EPMC9401866 | biostudies-literature
Unknown Peroxide Activation for Electrophilic Reactivity by the Binuclear Non-heme Iron Enzyme AurF.
| S-EPMC5843474 | biostudies-literature
Unknown A structure and reactivity analysis of monomeric Ni(II)-hydroxo complexes prepared from water.
| S-EPMC3863642 | biostudies-literature
Unknown Isolation and characterization of a high-spin mixed-valent iron dinitrogen complex.
| S-EPMC6258315 | biostudies-literature
Unknown Heme-Cu Binucleating Ligand Supports Heme/O2 and FeII-CuI/O2 Reactivity Providing High- and Low-Spin FeIII-Peroxo-CuII Complexes.
| S-EPMC6916717 | biostudies-literature