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Published December 15, 2014 | Supplemental Material
Journal Article Open

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

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.

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.

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