Nomrowski, Julia and Wenger, Oliver S.. (2015) Photoinduced PCET in Ruthenium−Phenol Systems : Thermodynamic Equivalence of Uni- and Bidirectional Reactions. Inorganic Chemistry, 54 (7). pp. 3680-3687.
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Official URL: http://edoc.unibas.ch/dok/A6381788
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Abstract
Six termolecular reaction systems comprised of Ru(4,4′-bis(trifluoromethyl)-2,2′-bipyridine)32+, phenols with different para substituents, and pyridine in acetonitrile undergo proton-coupled electron transfer (PCET) upon photoexcitation of the metal complex. Five of these six phenols are found to release in concerted fashion an electron to the ruthenium photooxidant and a proton to the pyridine base. The kinetics for this concerted bidirectional PCET process and its relationship to the reaction free energy were compared to the driving-force dependence of reaction kinetics for unidirectional concerted proton–electron transfer (CPET) between the same phenols and Ru(2,2′-bipyrazine)32+, a combined electron/proton acceptor. The results strongly support the concept of thermodynamic equivalence between separated electron/proton acceptors and single-reagent hydrogen-atom acceptors. A key feature of the explored systems is the similarity between molecules employed for bi- and unidirectional CPET.
Faculties and Departments: | 05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Wenger) |
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UniBasel Contributors: | Wenger, Oliver and Nomrowski, Julia |
Item Type: | Article, refereed |
Article Subtype: | Research Article |
Publisher: | American Chemical Society |
ISSN: | 0020-1669 |
e-ISSN: | 1520-510X |
Note: | Publication type according to Uni Basel Research Database: Journal article |
Identification Number: | |
Last Modified: | 03 May 2017 11:11 |
Deposited On: | 05 Jun 2015 08:53 |
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