Electrochemical study of a nonheme Fe(<scp>ii</scp>) complex in the presence of dioxygen. Insights into the reductive activation of O<sub>2</sub>at Fe(<scp>ii</scp>) centers

Ségaud, Nathalie; Anxolabéhère‐Mallart, Elodie; Sénéchal‐David, Katell; Acosta-Rueda, Laura; Robert, Marc; Banse, Frédéric

doi:10.1039/c4sc01891e

Cited by 33 publications

(61 citation statements)

References 61 publications

(77 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Recently in 2015, formation of iron(III)–peroxo and iron (IV)–oxo complexes were shown with the same ligand platform TPEN. 103 However, reductive activation of dioxygen in this case was achieved electrochemically.…”

Section: Dioxygen Activation By Nonheme Iron Complexesmentioning

confidence: 97%

Activation of Dioxygen by Iron and Manganese Complexes: A Heme and Nonheme Perspective

2016

View full text Add to dashboard Cite

The rational design of well-defined, first-row transition metal complexes that can activate dioxygen has been a challenging goal for the synthetic inorganic chemist. The activation of O2 is important in part because of its central role in the functioning of metalloenzymes, which utilize O2 to perform a number of challenging reactions including the highly selective oxidation of various substrates. There is also great interest in utilizing O2, an abundant and environmentally benign oxidant, in synthetic catalytic oxidation systems. This Perspective brings together recent examples of biomimetic Fe and Mn complexes that can activate O2 in heme or nonheme-type ligand environments. The use of oxidants such as hypervalent iodine (e.g., ArIO), peracids (e.g., m-CPBA), peroxides (e.g., H2O2) or even superoxide is a popular choice for accessing well-characterized metal–superoxo, metal–peroxo, or metal–oxo species, but the instances of biomimetic Fe/Mn complexes that react with dioxygen to yield such observable metal–oxygen species are surprisingly few. This Perspective focuses on mononuclear Fe and Mn complexes that exhibit reactivity with O2 and lead to spectroscopically observable metal–oxygen species, and/or oxidize biologically relevant substrates. Analysis of these examples reveals that solvent, spin state, redox potential, external co-reductants, and ligand architecture can all play important roles in the O2 activation process.

show abstract

Section: Dioxygen Activation By Nonheme Iron Complexesmentioning

confidence: 97%

Activation of Dioxygen by Iron and Manganese Complexes: A Heme and Nonheme Perspective

2016

View full text Add to dashboard Cite

show abstract

“…[28][29][30][31][32][33] Ther eactivity of iron-oxygen oxidants generated in the reductive activation of dioxygen by an iron(II)-benzilate complex, [(Tp Ph2 )Fe II (benzilate)] (1;T p Ph2 = hydrotris(3,5-diphenyl-pyrazol-1-yl)borate), has been investigated by us (Scheme 2). [28][29][30][31][32][33] Ther eactivity of iron-oxygen oxidants generated in the reductive activation of dioxygen by an iron(II)-benzilate complex, [(Tp Ph2 )Fe II (benzilate)] (1;T p Ph2 = hydrotris(3,5-diphenyl-pyrazol-1-yl)borate), has been investigated by us (Scheme 2).…”

mentioning

confidence: 99%

Hydroxylation versus Halogenation of Aliphatic C−H Bonds by a Dioxygen‐Derived Iron–Oxygen Oxidant: Functional Mimicking of Iron Halogenases

Chatterjee

Paine

2016

Angew Chem Int Ed

View full text Add to dashboard Cite

An iron-oxygen intermediate species generated in situ in the reductive activation of dioxygen by an iron(II)-benzilate complex of a monoanionic facial N3 ligand, promoted the halogenation of aliphatic C-H bonds in the presence of a protic acid and a halide anion. An electrophilic iron(IV)-oxo oxidant with a coordinated halide is proposed as the active oxidant. The halogenation reaction with dioxygen and the iron complex mimics the activity of non-heme iron halogenases.

show abstract

“…[15][16][17][18][19] Thepresence of "ready oxidant" H 2 O 2 and substrates together allows the complexes to catalyze the C À Hb ond hydroxylation and olefin cis-dihydroxylation through putative high-valent iron-oxo oxidants. [24][25][26][27][28][29][30][31][32] All these studies provide useful mechanistic information on reductive dioxygen activation by iron(II) complexes.H owever,examples of biomimetic iron complexes for oxidation of olefins and aliphatic substrates with dioxygen are rare. [24][25][26][27][28][29][30][31][32] All these studies provide useful mechanistic information on reductive dioxygen activation by iron(II) complexes.H owever,examples of biomimetic iron complexes for oxidation of olefins and aliphatic substrates with dioxygen are rare.…”

mentioning

confidence: 98%

Olefin cis‐Dihydroxylation and Aliphatic CH Bond Oxygenation by a Dioxygen‐Derived Electrophilic Iron–Oxygen Oxidant

Chatterjee

Paine

2015

Angewandte Chemie

View full text Add to dashboard Cite

Many iron-containing enzymes involve metaloxygen oxidants to carry out O 2 -dependent transformation reactions.H owever,t he selective oxidation of CÀHa nd C=C bonds by biomimetic complexes using O 2 remains am ajor challenge in bioinspired catalysis.T he reactivity of ironoxygen oxidants generated from an Fe II -benzilate complex of afacial N 3 ligand were thus investigated. The complex reacted with O 2 to form an ucleophilic oxidant, whereas an electrophilic oxidant, intercepted by external substrates,was generated in the presence of aL ewis acid. Based on the mechanistic studies,anucleophilic Fe II -hydroperoxo species is proposed to form from the benzilate complex, which undergoes heterolytic O À Obond cleavage in the presence of aLewis acid to generate an Fe IV -oxo-hydroxoo xidant. The electrophilic iron-oxygen oxidant selectively oxidizes sulfides to sulfoxides,a lkenes to cis-diols,a nd it hydroxylates the CÀHb onds of alkanes, including that of cyclohexane.

show abstract

Electrochemical study of a nonheme Fe(ii) complex in the presence of dioxygen. Insights into the reductive activation of O₂at Fe(ii) centers

Cited by 33 publications

References 61 publications

Activation of Dioxygen by Iron and Manganese Complexes: A Heme and Nonheme Perspective

Activation of Dioxygen by Iron and Manganese Complexes: A Heme and Nonheme Perspective

Hydroxylation versus Halogenation of Aliphatic C−H Bonds by a Dioxygen‐Derived Iron–Oxygen Oxidant: Functional Mimicking of Iron Halogenases

Olefin cis‐Dihydroxylation and Aliphatic CH Bond Oxygenation by a Dioxygen‐Derived Electrophilic Iron–Oxygen Oxidant

Contact Info

Product

Resources

About

Electrochemical study of a nonheme Fe(ii) complex in the presence of dioxygen. Insights into the reductive activation of O2at Fe(ii) centers

Cited by 33 publications

References 61 publications

Activation of Dioxygen by Iron and Manganese Complexes: A Heme and Nonheme Perspective

Activation of Dioxygen by Iron and Manganese Complexes: A Heme and Nonheme Perspective

Hydroxylation versus Halogenation of Aliphatic C−H Bonds by a Dioxygen‐Derived Iron–Oxygen Oxidant: Functional Mimicking of Iron Halogenases

Olefin cis‐Dihydroxylation and Aliphatic CH Bond Oxygenation by a Dioxygen‐Derived Electrophilic Iron–Oxygen Oxidant

Contact Info

Product

Resources

About

Electrochemical study of a nonheme Fe(ii) complex in the presence of dioxygen. Insights into the reductive activation of O₂at Fe(ii) centers