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Efficient C-H Bond Activations O_2 Cleavage by a Dianionic Cobalt(II) Complex

Nguyen, Andy I. and Hadt, Ryan G. and Solomon, Edward I. and Tilley, T. Don (2014) Efficient C-H Bond Activations O_2 Cleavage by a Dianionic Cobalt(II) Complex. Chemical Science, 5 (7). pp. 2874-2878. ISSN 2041-6520 . PMCID PMC4111274. http://resolver.caltech.edu/CaltechAUTHORS:20180612-111659936

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Abstract

A dianionic, square planar cobalt(II) complex reacts with O_2 in the presence of acetonitrile to give a cyanomethylcobalt(III) complex formed by C-H bond cleavage. Interestingly, PhIO and -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 pK_a 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 O_2 or PhIO. The possible involvement of a cobalt(IV) oxo species in this chemistry is discussed.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1039/C4SC00108GPublisherArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4111274/PubMed CentralArticle
ORCID:
AuthorORCID
Hadt, Ryan G.0000-0001-6026-1358
Solomon, Edward I.0000-0003-0291-3199
Tilley, T. Don0000-0002-6671-9099
Alternate Title:Efficient C-H Bond Activations O2 Cleavage by a Dianionic Cobalt(II) Complex.
Additional Information:© 2014 The Author(s). This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Received 10th January 2014. Accepted 7th May 2014. First published on 8th May 2014. This work was supported by the Director, Office of Science, Office of Basic Energy Sciences of the US Department of Energy under contract no. DE-AC02-05CH11231 and the National Institutes of Health (Grant GM 40392 to E.I.S.). R.G.H. acknowledges a Gerhard Casper Stanford Graduate Fellowship and the Achievement Rewards for College Scientist (ARCS) Foundation. The authors thank Dr Antonio Iavarone (QB3 Chemistry Mass Spectrometry Facility) for high-resolution ESI mass-spectrometry measurements, Apurva Pradhan for assistance with UV-vis measurements, and Dr John J. Curley for stimulating discussions.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE) DE-AC02-05CH11231
NIHGM40392
Stanford UniversityUNSPECIFIED
ARCS FoundationUNSPECIFIED
PubMed Central ID:PMC4111274
Record Number:CaltechAUTHORS:20180612-111659936
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20180612-111659936
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:87005
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:12 Jun 2018 18:28
Last Modified:12 Jun 2018 18:28

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