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C-H Bond Activation by Metal-Superoxo Species: What Drives High Reactivity?

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Title C-H Bond Activation by Metal-Superoxo Species: What Drives High Reactivity?
 
Creator ANSARI, A
JAYAPAL, P
RAJARAMAN, G
 
Subject COPPER-DIOXYGEN ADDUCT
NONHEME IRON COMPLEX
END-ON
CHROMIUM(III)-SUPEROXO COMPLEX
SPECTROSCOPIC CHARACTERIZATION
AROMATIC HYDROXYLATION
MECHANISTIC INSIGHTS
SYNTHETIC REAGENTS
MONONUCLEAR COPPER
OXYGEN ACTIVATION
CH activation
density functional calculations
iron
metalloenzymes
reaction mechanisms
 
Description Metal-superoxo species are ubiquitous in metalloenzymes and bioinorganic chemistry and are known for their high reactivity and their ability to activate inert CH bonds. The comparative oxidative abilities of M-O-2(.-) species (M=Cr-III, Mn-III, Fe-III, and Cu-II) towards CH bond activation reaction are presented. These superoxo species generated by oxygen activation are found to be aggressive oxidants compared to their high-valent metal-oxo counterparts generated by OO bond cleavage. Our calculations illustrate the superior oxidative abilities of Fe-III- and Mn-III-superoxo species compared to the others and suggest that the reactivity may be correlated to the magnetic exchange parameter.
 
Publisher WILEY-V C H VERLAG GMBH
 
Date 2016-01-14T10:22:21Z
2016-01-14T10:22:21Z
2015
 
Type Article
 
Identifier ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 54(2)564-568
1433-7851
1521-3773
http://dx.doi.org/10.1002/anie.201409844
http://dspace.library.iitb.ac.in/jspui/handle/100/17359
 
Language en