A Continuum of Proton-Coupled Electron Transfer Reactivity,Accounts of Chemical Research

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A Continuum of Proton-Coupled Electron Transfer Reactivity
Accounts of Chemical Research ( IF 16.4 ) Pub Date : 2018-09-20 00:00:00 , DOI: 10.1021/acs.accounts.8b00319
Julia W. Darcy ₁ , Brian Koronkiewicz ₁ , Giovanny A. Parada ₁ , James M. Mayer ₁

Affiliation

Proton-coupled electron transfer (PCET) covers a wide range of reactions involving the transfer(s) of electrons and protons. The best-known PCET reaction, hydrogen atom transfer (HAT), has been studied in detail for more than a century. HAT is generally described as the concerted transfer of a hydrogen atom (H^• ≡ H⁺ + e^–) from one group to another, Y + H–X → Y–H + X, but a strict definition of HAT has been difficult to establish. Distinctions are more challenging when the transfer of “H^•” involves e^– and H⁺ that transfer to/from spatially distinct sites or even completely separate reagents (multiple-site concerted proton–electron transfer, MS-CPET). MS-CPET reactivity is increasingly proposed in biological and synthetic contexts, and some reactions typically described as HAT more resemble MS-CPET. Despite that HAT and MS-CPET reactions “look different,” we argue here that these reactions lie on a reactivity continuum, and that they are governed by many of the same key parameters. This Account walks the reader across this PCET reactivity continuum, using a series of studies to show the strong similarities of reactions that move protons and electrons in seemingly different ways.

中文翻译：

质子耦合电子转移反应的连续性

质子耦合电子转移（PCET）涵盖了涉及电子和质子转移的广泛反应。最著名的PCET反应，氢原子转移（HAT），已经被研究了一个多世纪。HAT一般被描述为一个氢原子（H的协同传输^•＆equiv; H ^ ⁺ + ë ^-）从一个组至另一个，Y + H-X→Y-H + X，但HAT的严格定义一直难以建立。当“ H ^• ”的转移涉及e ^–和H ⁺时，区分更具挑战性。可以往返于空间上不同的位置或什至是完全分开的试剂（多位置协调的质子-电子转移，MS-CPET）。在生物学和合成环境中，越来越多地提出了MS-CPET反应性，通常被称为HAT的某些反应更类似于MS-CPET。尽管HAT和MS-CPET反应看起来“不同”，但我们在这里认为这些反应取决于反应性的连续性，并且它们受许多相同的关键参数支配。该帐户通过一系列研究显示了质子和电子以看似不同的方式移动的反应的强烈相似之处，使读者跨过了PCET反应性连续体。

更新日期：2018-09-20

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