title: C-H bond activation by metal-superoxo species: what drives high reactivity?
abstract: 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.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, Maharashtra, 400076 (India) http://www.chem.iitb.ac.in/people/Faculty/prof/gr.html.
authors.forename: Azaj
authors.initials: A
authors.lastname: Ansari
authors.forename: Prabha
authors.initials: P
authors.lastname: Jayapal
authors.forename: Gopalan
authors.initials: G
authors.lastname: Rajaraman
mesh_terms: D002244:Carbon / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D008670:Metals / Q000737:chemistry*; D013481:Superoxides / Q000737:chemistry*
chemical_list: D008670:Metals; D013481:Superoxides; D002244:Carbon; D006859:Hydrogen
keywords: CH activation; density functional calculations; iron; metalloenzymes; reaction mechanisms