C-H bond activation by metal-superoxo species: what drives high reactivity?
Azaj Ansari1, Prabha Jayapal, Gopalan Rajaraman
1Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, Maharashtra, 400076 (India) http://www.chem.iitb.ac.in/people/Faculty/prof/gr.html.
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.
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