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CH Bond Activation by Metal–Superoxo Species: What Drives High Reactivity?
Author(s) -
Ansari Azaj,
Jayapal Prabha,
Rajaraman Gopalan
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201409844
Subject(s) - reactivity (psychology) , chemistry , bond cleavage , metal , bioinorganic chemistry , oxidative addition , photochemistry , cleavage (geology) , medicinal chemistry , stereochemistry , catalysis , organic chemistry , materials science , medicine , alternative medicine , pathology , fracture (geology) , composite material
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 O⋅⋅⋅O 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.