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Reactivity of a Series of Isostructural Cobalt Pincer Complexes with CO_2, CO, and H^+

Shaffer, David W. and Johnson, Samantha I. and Rheingold, Arnold L. and Ziller, Joseph W. and Goddard, William A., III and Nielsen, Robert J. and Yang, Jenny Y. (2014) Reactivity of a Series of Isostructural Cobalt Pincer Complexes with CO_2, CO, and H^+. Inorganic Chemistry, 53 (24). pp. 13031-13041. ISSN 0020-1669. https://resolver.caltech.edu/CaltechAUTHORS:20150122-111631531

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Abstract

The preparation and characterization of a series of isostructural cobalt complexes Co(t-Bu)_2(P^EPy^EP)(t-Bu)_2(CH_3CN)_2]-[BF_4]_2 (Py = pyridine, E = CH_2, NH, O, and X = BF_4 (1a-c)) and the corresponding one-electron reduced analogues Co(t-Bu)_2P^EPy^EP(t-Bu)_2(CH_3CN)_2][BF_4]_2 (2a-c) are reported. The reactivity of the reduced cobalt complexes with CO_2, CO, and H^+ to generate intermediates in a CO_2 to CO and H_2O reduction cycle are described. The reduction of 1a-c and subsequent reactivity with CO_2 was investigated by cyclic voltammetry, and for 1a also by infrared spectroelectrochemistry. The corresponding CO complexes of (2a-c) were prepared, and the Co-CO bond strengths were characterized by IR spectroscopy. Quantum mechanical methods (B3LYP-d3 with solvation) were used to characterize the competitive reactivity of the reduced cobalt centers with H^+ versus CO_2. By investigating a series of isostructural complexes, correlations in reactivity with ligand electron withdrawing effects are made.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ic5021725DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ic5021725PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ic5021725PublisherSupporting Information
ORCID:
AuthorORCID
Rheingold, Arnold L.0000-0003-4472-8127
Goddard, William A., III0000-0003-0097-5716
Nielsen, Robert J.0000-0002-7962-0186
Alternate Title:Reactivity of a Series of Isostructural Cobalt Pincer Complexes with CO2, CO, and H+
Additional Information:© 2014 American Chemical Society. Received: September 8, 2014. Publication Date (Web): December 3, 2014. This material is based upon work performed at the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC0004993, and additional support from the School of Physical Sciences at the University of California, Irvine. S.I.J. would like to acknowledge support from the National Science Foundation Graduate Research Fellowship under Grant DGE# 1144469. The authors thank C. Tsay and L. Henling for helpful discussions and assistance.
Group:JCAP
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
University of California, IrvineUNSPECIFIED
NSF Graduate Research FellowshipDGE-1144469
Issue or Number:24
Record Number:CaltechAUTHORS:20150122-111631531
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150122-111631531
Official Citation:Reactivity of a Series of Isostructural Cobalt Pincer Complexes with CO2, CO, and H+ David W. Shaffer, Samantha I. Johnson, Arnold L. Rheingold, Joseph W. Ziller, William A. Goddard, III, Robert J. Nielsen, and Jenny Y. Yang Inorganic Chemistry 2014 53 (24), 13031-13041
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:53992
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:22 Jan 2015 20:42
Last Modified:09 Mar 2020 13:19

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