Finding the Reactive Electron in Paramagnetic Systems: A Critical Evaluation of Accuracies for EPR Spectroscopy and Density Functional Theory Using 1,3,5-Triphenyl Verdazyl Radical as a Testcase

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• 作者：Jessica Barilone (1)
  Frank Neese (1)
  Maurice van Gastel (1)
  
  1. Max Planck Institute for Chemical Energy Conversion ; Stiftstrasse 34-36 ; 45470 ; M眉lheim an der Ruhr ; Germany
  
• 刊名：Applied Magnetic Resonance
• 出版年：2015
• 出版时间：February 2015
• 年：2015
• 卷：46
• 期：2
• 页码：117-139
• 全文大小：624 KB
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• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Analytical Chemistry
  
• 出版者：Springer Wien
• ISSN：1613-7507

文摘

One of the biggest challenges in studying catalytic reactions is characterizing intermediate states and identifying reaction pathways. Oftentimes, intermediate states with unpaired electrons are formed which provide an opportunity to study the compound via electron paramagnetic resonance (EPR). Combining EPR with density functional theory (DFT) represents a powerful synergistic approach to accomplish these goals. Once the catalytic intermediates and reaction pathway are known, rate-limiting steps critical to parameters like overpotential and turnover number may be identified and eliminated. In this study 1,3,5-triphenyl verdazyl is examined using continuous-wave-EPR, electron nuclear double resonance and DFT as an instructive example of how theory and experiment can complement each other to find the reactive electron. The methods and concomitant analysis have been presented in didactic fashion and with emphasis on the strengths and weaknesses of the methods.