Enzymatic C-H activation by metal-superoxo intermediates

Research output: Contribution to journalReview article

106 Citations (Scopus)

Abstract

The mechanisms of four enzymes that initiate oxidation of their substrates by using mid-valent metal-superoxo intermediates, rather than the more frequently described high-valent iron-oxo complexes, to cleave relatively strong C-H bonds have come into focus in the past several years. In two of these reactions, the alternative manifold for O2 and C-H activation enables unique four-electron oxidation reactions, thus significantly augmenting Nature's arsenal for transformation of aliphatic carbon compounds. General principles of this alternative manifold, including common kinetic characteristics and thermodynamic limitations, are emerging. Recent, combined experimental and computational studies on other systems have shown how a more thorough understanding of the structures of the metal-superoxo intermediates and the mechanisms by which they cleave C-H bonds might be achieved.

Original languageEnglish (US)
Pages (from-to)151-158
Number of pages8
JournalCurrent Opinion in Chemical Biology
Volume11
Issue number2
DOIs
StatePublished - Apr 1 2007

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Metalloids
Metals
Chemical activation
Arsenals
Oxidation
Thermodynamics
Carbon
Iron
Electrons
Kinetics
Substrates
Enzymes

All Science Journal Classification (ASJC) codes

  • Analytical Chemistry
  • Biochemistry

Cite this

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title = "Enzymatic C-H activation by metal-superoxo intermediates",
abstract = "The mechanisms of four enzymes that initiate oxidation of their substrates by using mid-valent metal-superoxo intermediates, rather than the more frequently described high-valent iron-oxo complexes, to cleave relatively strong C-H bonds have come into focus in the past several years. In two of these reactions, the alternative manifold for O2 and C-H activation enables unique four-electron oxidation reactions, thus significantly augmenting Nature's arsenal for transformation of aliphatic carbon compounds. General principles of this alternative manifold, including common kinetic characteristics and thermodynamic limitations, are emerging. Recent, combined experimental and computational studies on other systems have shown how a more thorough understanding of the structures of the metal-superoxo intermediates and the mechanisms by which they cleave C-H bonds might be achieved.",
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Enzymatic C-H activation by metal-superoxo intermediates. / Bollinger, Jr., Joseph M.; Krebs, Carsten.

In: Current Opinion in Chemical Biology, Vol. 11, No. 2, 01.04.2007, p. 151-158.

Research output: Contribution to journalReview article

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T1 - Enzymatic C-H activation by metal-superoxo intermediates

AU - Bollinger, Jr., Joseph M.

AU - Krebs, Carsten

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AB - The mechanisms of four enzymes that initiate oxidation of their substrates by using mid-valent metal-superoxo intermediates, rather than the more frequently described high-valent iron-oxo complexes, to cleave relatively strong C-H bonds have come into focus in the past several years. In two of these reactions, the alternative manifold for O2 and C-H activation enables unique four-electron oxidation reactions, thus significantly augmenting Nature's arsenal for transformation of aliphatic carbon compounds. General principles of this alternative manifold, including common kinetic characteristics and thermodynamic limitations, are emerging. Recent, combined experimental and computational studies on other systems have shown how a more thorough understanding of the structures of the metal-superoxo intermediates and the mechanisms by which they cleave C-H bonds might be achieved.

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