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Photoinduced PCET in Ruthenium−Phenol Systems : Thermodynamic Equivalence of Uni- and Bidirectional Reactions

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)
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
Language:English
Identification Number:
Last Modified:06 Jun 2018 13:45
Deposited On:05 Jun 2015 08:53

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