Rose, Michael J. and Gray, Harry B. and Winkler, Jay R. (2012) Hydrogen Generation Catalyzed by Fluorinated Diglyoxime−Iron Complexes at Low Overpotentials. Journal of the American Chemical Society, 134 (20). pp. 8310-8313. ISSN 0002-7863. doi:10.1021/ja300534r. https://resolver.caltech.edu/CaltechAUTHORS:20120621-073446298
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Abstract
Fe^(II) complexes containing the fluorinated ligand 1,2-bis(perfluorophenyl)ethane-1,2-dionedioxime (dAr^FgH_2; H = dissociable proton) exhibit relatively positive Fe^(II/I) reduction potentials. The air-stable difluoroborated species [(dAr^FgBF_2)_2Fe(py)_2] (2) electrocatalyzes H_2 generation at −0.9 V vs SCE with i_(cat)/i_p ≈ 4, corresponding to a turnover frequency (TOF) of ~ 20 s^(–1) [Faradaic yield (FY) = 82 ± 13%]. The corresponding monofluoroborated, proton-bridged complex [(dArFg2H-BF2)Fe(py)2] (3) exhibits an improved TOF of ~ 200 s^(–1) (i_(cat)/i_p ≈ 8; FY = 68 ± 14%) at −0.8 V with an overpotential of 300 mV. Simulations of the electrocatalytic cyclic voltammograms of 2 suggest rate-limiting protonation of an Fe“0” intermediate (k_(RLS) ≈ 200 M^(–1) s^(–1)) that undergoes hydride protonation to form H_2. Complex 3 likely reacts via protonation of an Fe^I intermediate that subsequently forms H_2 via a bimetallic mechanism (k_(RLS) ≈ 2000 M^(–1) s^(–1)). 3 catalyzes production at relatively positive potentials compared with other iron complexes.
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| Additional Information: | © 2012 American Chemical Society. Received: January 17, 2012. Publication Date (Web): May 14, 2012. This work was supported by the NSF CCI Solar Fuels Program (CHE-0802907). M.J.R. was supported by an NSF ACC-F Fellowship (CHE-1042009). The Bruker APEXII diffractometer was obtained via an NSF CRIF:MU Award (CHE-0639094). We thank Larry Henling and Michael Day for solving the crystal structures. | |||||||||
| Group: | CCI Solar Fuels | |||||||||
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| Issue or Number: | 20 | |||||||||
| DOI: | 10.1021/ja300534r | |||||||||
| Record Number: | CaltechAUTHORS:20120621-073446298 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20120621-073446298 | |||||||||
| Official Citation: | Hydrogen Generation Catalyzed by Fluorinated Diglyoxime–Iron Complexes at Low Overpotentials Michael J. Rose, Harry B. Gray, and Jay R. Winkler Journal of the American Chemical Society 2012 134 (20), 8310-8313 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 31996 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Ruth Sustaita | |||||||||
| Deposited On: | 21 Jun 2012 14:57 | |||||||||
| Last Modified: | 09 Nov 2021 20:02 |
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