CH Bond Activation by Metal–Superoxo Species: What Drives High Reactivity?1. (21st November 2014)

• Record Type: Journal Article
• Authors: Ansari, Azaj; Jayapal, Prabha; Rajaraman, Gopalan
• Is Part Of: Angewandte Chemie. Volume 127:Number 2(2015)
• Page Start: 574
• Page End: 578
• Publication Date: 2014-11-21
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201409844
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Metal–superoxo species are ubiquitous in metalloenzymes and bioinorganic chemistry and are known for their high reactivity and their ability to activate inert CH bonds. The comparative oxidative abilities of M–O₂^.− species (M=Cr^III, Mn^III, Fe^III, and Cu^II) towards CH 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.</p> </abstract>