Dataset Information

A Mononuclear Nonheme Iron(V)-Imido Complex.

ABSTRACT: Mononuclear nonheme iron(V)-oxo complexes have been reported previously. Herein, we report the first example of a mononuclear nonheme iron(V)-imido complex bearing a tetraamido macrocyclic ligand (TAML), [(TAML)FeV(NTs)]- (1). The spectroscopic characterization of 1 revealed an S = 1/2 Fe(V) oxidation state, an Fe-N bond length of 1.65(4) Å, and an Fe-N vibration at 817 cm-1. The reactivity of 1 was demonstrated in C-H bond functionalization and nitrene transfer reactions.

SUBMITTER: Hong S

PROVIDER: S-EPMC5843466 | biostudies-literature | 2017 Jul

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

A Mononuclear Nonheme Iron(V)-Imido Complex.

Hong Seungwoo S Sutherlin Kyle D KD Vardhaman Anil Kumar AK Yan James J JJ Park Sora S Lee Yong-Min YM Jang Soojeong S Lu Xiaoyan X Ohta Takehiro T Ogura Takashi T Solomon Edward I EI Nam Wonwoo W

Journal of the American Chemical Society 20170623 26

Mononuclear nonheme iron(V)-oxo complexes have been reported previously. Herein, we report the first example of a mononuclear nonheme iron(V)-imido complex bearing a tetraamido macrocyclic ligand (TAML), [(TAML)FeV(NTs)]- (1). The spectroscopic characterization of 1 revealed an S = 1/2 Fe(V) oxidation state, an Fe-N bond length of 1.65(4) Å, and an Fe-N vibration at 817 cm-1. The reactivity of 1 was demonstrated in C-H bond functionalization and nitrene transfer ...[more]

PMID: 28628312

Similar Datasets

Project description:Redox-inactive metal ions that function as Lewis acids play pivotal roles in modulating reactivities of oxygen-containing metal complexes in a variety of biological and biomimetic reactions, including dioxygen activation/formation and functionalization of organic substrates. Mononuclear nonheme iron(III)-peroxo species are invoked as active oxygen intermediates in the catalytic cycles of dioxygen activation by nonheme iron enzymes and their biomimetic compounds. Here, we report mononuclear nonheme iron(III)-peroxo complexes binding redox-inactive metal ions, [(TMC)FeIII(O2)]+-M3+ (M3+ = Sc3+ and Y3+; TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), which are characterized spectroscopically as a 'side-on' iron(III)-peroxo complex binding a redox-inactive metal ion, (TMC)FeIII-(?,?2:?2-O2)-M3+ (2-M). While an iron(III)-peroxo complex, [(TMC)FeIII(O2)]+, does not react with electron donors (e.g., ferrocene), one-electron reduction of the iron(III)-peroxo complexes binding redox-inactive metal ions occurs readily upon addition of electron donors, resulting in the generation of an iron(IV)-oxo complex, [(TMC)FeIV(O)]2+ (4), via heterolytic O-O bond cleavage of the peroxide ligand. The rates of the conversion of 2-M to 4 are found to depend on the Lewis acidity of the redox-inactive metal ions and the oxidation potential of the electron donors. We have also determined the fundamental electron-transfer properties of 2-M, such as the reduction potential and the reorganization energy in electron-transfer reaction. Based on the results presented herein, we have proposed a mechanism for the reactions of 2-M and electron donors; the reduction of 2-M to the reduced species, (TMC)FeII-(O2)-M3+ (2'-M), is the rate-determining step, followed by heterolytic O-O bond cleavage of the reduced species to form 4. The present results provide a biomimetic example demonstrating that redox-inactive metal ions bound to an iron(III)-peroxo intermediate play a significant role in activating the peroxide O-O bond to form a high-valent iron(IV)-oxo species.

Dataset Information

A Mononuclear Nonheme Iron(V)-Imido Complex.

Publications

A Mononuclear Nonheme Iron(V)-Imido Complex.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets