Reconciling Imbalanced and Nonadiabatic Reactivity in Transition Metal–Oxo-Mediated Concerted Proton Electron Transfer (CPET)

IF 4.8 2区 化学 Q2 CHEMISTRY, PHYSICAL
Joseph E. Schneider,  and , John S. Anderson*, 
{"title":"Reconciling Imbalanced and Nonadiabatic Reactivity in Transition Metal–Oxo-Mediated Concerted Proton Electron Transfer (CPET)","authors":"Joseph E. Schneider,&nbsp; and ,&nbsp;John S. Anderson*,&nbsp;","doi":"10.1021/acs.jpclett.3c02318","DOIUrl":null,"url":null,"abstract":"<p >Recently, there have been several experimental demonstrations of how the rates of concerted proton electron transfer (CPET) are affected by stepwise thermodynamic parameters of only proton (Δ<i>G</i>°<sub>PT</sub>) or electron (Δ<i>G</i>°<sub>ET</sub>) transfer. Semiclassical structure–activity relationships have been invoked to rationalize these linear free energy relationships, but it is not clear how they would manifest in a nonadiabatic reaction. Using density functional theory calculations, we demonstrate how a decrease in Δ<i>G</i>°<sub>PT</sub> can lead to transition state imbalance in a nonadiabatic framework. We then use these calculations to anchor a theoretical model that reproduces experimental trends with Δ<i>G</i>°<sub>PT</sub> and Δ<i>G</i>°<sub>ET</sub>. Our results reconcile predictions from semiclassical transition state theory with models that treat proton transfer quantum mechanically in CPET reactivity, make new predictions about the importance of basicity for uphill CPET reactions, and suggest similar treatments may be possible for other nonadiabatic reactions.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"14 43","pages":"9548–9555"},"PeriodicalIF":4.8000,"publicationDate":"2023-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry Letters","FirstCategoryId":"1","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.jpclett.3c02318","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0

Abstract

Recently, there have been several experimental demonstrations of how the rates of concerted proton electron transfer (CPET) are affected by stepwise thermodynamic parameters of only proton (ΔG°PT) or electron (ΔG°ET) transfer. Semiclassical structure–activity relationships have been invoked to rationalize these linear free energy relationships, but it is not clear how they would manifest in a nonadiabatic reaction. Using density functional theory calculations, we demonstrate how a decrease in ΔG°PT can lead to transition state imbalance in a nonadiabatic framework. We then use these calculations to anchor a theoretical model that reproduces experimental trends with ΔG°PT and ΔG°ET. Our results reconcile predictions from semiclassical transition state theory with models that treat proton transfer quantum mechanically in CPET reactivity, make new predictions about the importance of basicity for uphill CPET reactions, and suggest similar treatments may be possible for other nonadiabatic reactions.

Abstract Image

过渡金属氧介导的协同质子-电子转移(CPET)中不平衡和非绝热反应性的协调。
最近,已经有几项实验证明了协同质子-电子转移(CPET)的速率如何受到仅质子(ΔG°PT)或电子(ΔG±ET)转移的逐步热力学参数的影响。半经典的结构-活性关系已被用来合理化这些线性自由能关系,但尚不清楚它们将如何在非绝热反应中表现出来。使用密度泛函理论计算,我们证明了ΔG°PT的降低如何导致非绝热框架中的过渡态不平衡。然后,我们使用这些计算来锚定一个理论模型,该模型再现了ΔG°PT和ΔG°ET的实验趋势。我们的结果将半经典过渡态理论的预测与在CPET反应性中以机械方式处理质子转移量子的模型相协调,对碱性对上坡CPET反应的重要性做出了新的预测,并表明类似的处理可能适用于其他非绝热反应。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 求助全文
来源期刊
The Journal of Physical Chemistry Letters
The Journal of Physical Chemistry Letters CHEMISTRY, PHYSICAL-NANOSCIENCE & NANOTECHNOLOGY
CiteScore
9.60
自引率
7.00%
发文量
1519
审稿时长
1.6 months
期刊介绍: The Journal of Physical Chemistry (JPC) Letters is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, chemical physicists, physicists, material scientists, and engineers. An important criterion for acceptance is that the paper reports a significant scientific advance and/or physical insight such that rapid publication is essential. Two issues of JPC Letters are published each month.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信