Speeding Up Oxygen Atom Transfer Reactions

  • ChemPubSoc Europe Logo
  • Author: Angewandte Chemie International Edition
  • Published Date: 17 April 2017
  • Source / Publisher: Angewandte Chemie International Edition/Wiley-VCH
  • Copyright: Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
thumbnail image: Speeding Up Oxygen Atom Transfer Reactions

Oxygen atom transfer (OAT) is common in many biological transformations and synthetic organic methods, where high-valent metal-oxo species are key intermediates. The oxygen-evolving complex of photosystem II, a multinuclear enzyme active site responsible for biological water oxidation, is also proposed to contain reactive metal-oxo moieties. Investigating redox changes in synthetic clusters and their influence on OAT at remote metal centers can provide valuable information regarding structure-function relationships relevant to biological systems.


Theodor Agapie, California Institute of Technology (Caltech), Pasadena, CA, USA, and colleagues have prepared a series of metal clusters with oxidation states that differ by a single electron (FeIII2FeIIMnII vs. FeIII3MnII). Remarkable differences in the rate of intramolecular C−H bond oxygenation of 2-(tert-butylsulfonyl)-iodosobenzene (sPhIO) were observed for these clusters.


These differences were attributed to the reactivity of iodosobenzene-metal adducts. FeIII3MnII-OIsPh (pictured right) is one of the very few examples of such species characterized by single crystal X-ray diffraction. These results provide new insights regarding the effect of redox state and electron distribution within biomimetic transition-metal clusters on their reactivity.


 

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