Issue 7, 2014

Efficient C–H bond activations via O2 cleavage by a dianionic cobalt(ii) complex

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.

Graphical abstract: Efficient C–H bond activations via O2 cleavage by a dianionic cobalt(ii) complex

Supplementary files

Article information

Article type
Edge Article
Submitted
10 Jan 2014
Accepted
07 May 2014
First published
08 May 2014
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2014,5, 2874-2878

Efficient C–H bond activations via O2 cleavage by a dianionic cobalt(II) complex

A. I. Nguyen, R. G. Hadt, E. I. Solomon and T. D. Tilley, Chem. Sci., 2014, 5, 2874 DOI: 10.1039/C4SC00108G

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements