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Dioxygen-Derived Nonheme Mononuclear Fe^III(OH) Complex and Its Reactivity with Carbon Radicals.

ABSTRACT: A new tetradentate, monoanionic, mixed N/O donor ligand (BNPA^Ph2O^-) with second coordination sphere H-bonding groups has been synthesized for stabilization of a terminal Fe^III(OH) complex. The complex Fe^II(BNPA^Ph2O)(OTf) (1) reacts with O₂ to give a mononuclear terminal Fe^III(OH) complex, Fe^III(OH)(BNPA^Ph2O)(OTf) (2), both of which were characterized by X-ray diffraction, electrospray ionization mass spectrometry, UV-vis, ¹H and ¹⁹F nuclear magnetic resonance, ⁵⁷Fe Mössbauer, and electron paramagnetic resonance spectroscopies. Treatment of 2 with carbon radicals (Ar₃C·) gives Ar₃COH and the Fe^II complex 1, in direct analogy with the elusive radical "rebound" process proposed for nonheme iron enzymes.

SUBMITTER: Yadav V

PROVIDER: S-EPMC8006860 | biostudies-literature | 2019 Jul

REPOSITORIES: biostudies-literature

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Dioxygen-Derived Nonheme Mononuclear FeIII(OH) Complex and Its Reactivity with Carbon Radicals.

Yadav Vishal V Gordon Jesse B JB Siegler Maxime A MA Goldberg David P DP

Journal of the American Chemical Society 20190620 26

A new tetradentate, monoanionic, mixed N/O donor ligand (BNPAPh2O-) with second coordination sphere H-bonding groups has been synthesized for stabilization of a terminal FeIII(OH) complex. The complex FeII(BNPAPh2O)(OTf) (1) reacts with O2 to give a mononuclear terminal FeIII(OH) complex, FeIII(OH)(BNPAPh2O)(OTf) (2), both of which were characterized by X-ray diffraction, electrospray ionization ma ...[more]

PMID: 31244183

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