A new look at the role of thiolate ligation in cytochrome P450

Yosca, Timothy H.; Ledray, Aaron P.; Ngo, J.; Green, Michael T.

doi:10.1007/s00775-016-1430-3

Cited by 73 publications

(83 citation statements)

References 79 publications

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“…1 One notable example is the O 2 -activation by iron-containing heme and nonheme enzymes, in which iron–oxygen intermediates have been trapped and characterized using various spectroscopic techniques. 2,3 In biomimetic studies, a large number of iron–oxygen intermediates bearing porphyrin and nonporphyrin ligands have been successfully synthesized as the model compounds of the heme and nonheme iron enzymes, and their chemical properties as well as the mechanisms of the formation of the iron–oxygen intermediates have been elucidated using the model compounds. 4,5 In most of the model studies, artificial oxidants, such as iodosylbenzene (PhIO), peracids, NaOCl, H 2 O 2 , and alkyl hydroperoxides, have been used as surrogates for O 2 for the synthesis of the iron–oxygen intermediates.…”

Section: Introductionmentioning

confidence: 99%

Dioxygen Activation and O–O Bond Formation Reactions by Manganese Corroles

et al. 2017

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Activation of dioxygen (O2) in enzymatic and biomimetic reactions has been intensively investigated over the past several decades. More recently, O–O bond formation, which is the reverse of the O2-activation reaction, has been the focus of current research. Herein, we report the O2-activation and O–O bond formation reactions by manganese corrole complexes. In the O2-activation reaction, Mn(V)-oxo and Mn(IV)-peroxo intermediates were formed when Mn(III) corroles were exposed to O2 in the presence of base (e.g., OH−) and hydrogen atom (H atom) donor (e.g., THF or cyclic olefins); the O2-activation reaction did not occur in the absence of base and H atom donor. Moreover, formation of the Mn(V)-oxo and Mn(IV)-peroxo species was dependent on the amounts of base present in the reaction solution. The role of the base was proposed to lower the oxidation potential of the Mn(III) corroles, thereby facilitating the binding of O2 and forming a Mn(IV)-superoxo species. The putative Mn(IV)-superoxo species was then converted to the corresponding Mn(IV)-hydroperoxo species by abstracting a H atom from H atom donor, followed by the O–O bond cleavage of the putative Mn(IV)-hydroperoxo species to form a Mn(V)-oxo species. We have also shown that addition of hydroxide ion to the Mn(V)-oxo species afforded the Mn(IV)-peroxo species via O–O bond formation and the resulting Mn(IV)-peroxo species reverted to the Mn(V)-oxo species upon addition of proton, indicating that the O–O bond formation and cleavage reactions between the Mn(V)-oxo and Mn(IV)-peroxo complexes are reversible. The present study reports the first example of using the same manganese complex in both O2-activation and O–O bond formation reactions.

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Section: Introductionmentioning

confidence: 99%

Dioxygen Activation and O–O Bond Formation Reactions by Manganese Corroles

et al. 2017

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“…[15] In the thiolate-ligated haem groups, which include cytochrome P450 and chloroperoxidase, the O ligand was found to be protonated, constituting an Fe IV -OH species. [15,16]…”

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confidence: 99%

Synthetic High‐Valent M–O–X Oxidants

Pirovano

McDonald

2018

Eur J Inorg Chem

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High‐valent metal–oxygen species (M–O–X species, as opposed to terminal metal‐oxo, M=O, species) have been found to constitute a large family of capable oxidants. Herein, synthetic high‐valent complexes with hydroxide, alkoxide and other anionic O‐atom ligands, as well as O–Lewis acid adducts, are reviewed with a focus on their reactivity. Mn, Fe and Ru complexes are described, as well as recent additions to the field containing late transition metals (Co, Ni, Cu). These species are competent in a range of oxidations, and in particular they are capable of hydrogen atom transfer from strong C–H bonds. We explore how their reaction mechanisms and oxidising potency are modulated by the O‐atom ligand.

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“…3 The one-electron oxidized species, 2 , showed slightly increased reactivity in amination reaction (i.e., ~2.5 times increase) but markedly enhanced reactivity in nitrene transfer reaction (i.e., ~17 000 times increase). Future studies will focus on detailed mechanisms and reactivity comparison of 1 and 2 in various oxidation reactions.…”

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confidence: 99%

Achieving One-Electron Oxidation of a Mononuclear Nonheme Iron(V)-Imido Complex

et al. 2017

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A mononuclear nonheme iron(V)-imido complex bearing a tetraamido macrocyclic ligand (TAML), [FeV(NTs)(TAML)]− (1), was oxidized by one-electron oxidants, affording formation of an iron(V)-imido TAML cation radical species, [FeV(NTs)(TAML+•)] (2); 2 is a diamagnetic (S = 0) complex, resulting from the antiferromagnetic coupling of the low-spin iron(V) ion (S = 1/2) with the one-electron oxidized ligand (TAML+•). 2 is a competent oxidant in C–H bond functionalization and nitrene transfer reaction, showing that the reactivity of 2 is greater than that of 1.

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A new look at the role of thiolate ligation in cytochrome P450

Cited by 73 publications

References 79 publications

Dioxygen Activation and O–O Bond Formation Reactions by Manganese Corroles

Dioxygen Activation and O–O Bond Formation Reactions by Manganese Corroles

Synthetic High‐Valent M–O–X Oxidants

Achieving One-Electron Oxidation of a Mononuclear Nonheme Iron(V)-Imido Complex

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