Rate–Driving Force Relationships in the Multisite Proton-Coupled Electron Transfer Activation of Ketones
نویسندگان
چکیده
منابع مشابه
Proton-coupled electron transfer.
Proton-coupled electron transfer (PCET) is an important mechanism for charge transfer in a wide variety of systems including biology- and materials-oriented venues. We review several areas where the transfer of an electron and proton is tightly coupled and discuss model systems that can provide an experimental basis for a test of PCET theory. In a PCET reaction, the electron and proton may tran...
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The kinetics of proton-coupled electron-transfer (pcet) reactions are reported for Mn4O4(O2PPh2)6, 1, and [Mn4O4(O2PPh2)6] , 1 , with phenothiazine (pzH). Both pcet reactions form 1H, by H transfer to 1 and by hydride transfer to 1 . Surprisingly, the rate constants differ by only 25% despite large differences in the formal charges and driving force. The driving force is proportional to the dif...
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A comparative theoretical investigation of single electron transfer (ET), single proton transfer (PT), and proton-coupled electron transfer (PCET) reactions in iron bi-imidazoline complexes is presented. These calculations are motivated by experimental studies showing that the rates of ET and PCET are similar and are both slower than the rate of PT for these systems (Roth, J. P.; Lovel, S.; May...
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Proton-coupled electron transfer (PCET) reactions play an essential role in a broad range of energy conversion processes, including photosynthesis and respiration. These reactions also form the basis of many types of solar fuel cells and electrochemical devices. Recent advances in the theory of PCET enable the prediction of the impact of system properties on the reaction rates. These prediction...
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The selective reduction of oxygen to water requires four electrons and four protons. The design of catalysts that promote oxygen reduction therefore requires the management of both electron and proton inventories. Pacman and Hangman porphyrins provide a cleft for oxygen binding, a redox shuttle for oxygen reduction, and functionality for tuning the acid-base properties of bound oxygen and its i...
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ژورنال
عنوان ژورنال: Journal of the American Chemical Society
سال: 2019
ISSN: 0002-7863,1520-5126
DOI: 10.1021/jacs.8b13451