Efficient C-H Bond Activations via O2 Cleavage by a Dianionic Cobalt(II) Complex.
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ABSTRACT: A dianionic, square planar cobalt(II) complex reacts with O2 in the presence of acetonitrile to give a cyanomethylcobalt(III) complex formed by C-H bond cleavage. Interestingly, PhIO and p-tolylazide react similarly to give the same cyanomethylcobalt(III) complex. Competition studies with various hydrocarbon substrates indicate that the rate of C-H bond cleavage greatly depends on the p Ka of the C-H bond, rather than on the C-H bond dissociation energy. Kinetic isotope experiments reveal a moderate KIE value of ca. 3.5 using either O2 or PhIO. The possible involvement of a cobalt(IV) oxo species in this chemistry is discussed.
SUBMITTER: Nguyen AI
PROVIDER: S-EPMC4111274 | biostudies-literature |
REPOSITORIES: biostudies-literature
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