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Royal Society of Chemistry, Chemical Science, 7(5), p. 2874-2878

DOI: 10.1039/c4sc00108g

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Efficient C–H bond activations via O2cleavage by a dianionic cobalt(ii) complex

Journal article published in 2014 by Andy I. Nguyen ORCID, Ryan G. Hadt, Edward I. Solomon, T. Don Tilley
This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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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-tolyl azide 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 pKa 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.