4.5 Article

DFT as a Powerful Predictive Tool in Photoredox Catalysis: Redox Potentials and Mechanistic Analysis

期刊

ORGANOMETALLICS
卷 34, 期 17, 页码 4218-4228

出版社

AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.5b00582

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资金

  1. Research Council of Norway [179568]
  2. European Research Council [279619]
  3. Department of Chemistry at UiT - The Arctic University of Norway
  4. Norwegian super-computing program NOTUR [NN4654K]
  5. European Research Council (ERC) [279619] Funding Source: European Research Council (ERC)

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Visible-light photoredox catalysis has come forth as a powerful activation mode in chemical synthesis, affording the development of a multitude of new strategies for molecular construction. However, detailed mechanistic knowledge of the various subprocesses involved is lacking, and new tools for addressing this are needed to drive innovation forward in the area. Herein, we describe predictions of ground-and excited-state redox potentials of ruthenium and iridium photocatalysts using nonrelativistic and scalar relativistic zero-order regular approximation density functional theory (DFT) methods. The computed redox potentials were correlated with experimental values and found to reproduce them well. Relativistic corrections were found to be important to reproduce experimental data. Moreover, the computational protocol allows us to estimate redox potentials that are not currently available in the literature or are difficult to determine experimentally. The mechanistic details of the photocatalyzed C-H functionalization of I-methylindole with diethyl bromomalonate were also studied using the validated DFT method. We demonstrate how DFT can predict the experimentally observed redox behavior of common photocatalysts and mechanistic details of the C-H functionalization process. This work demonstrates that DFT can be a powerful tool for innovation and design in the field of visible-light photoredox catalysis by predicting redox properties and mechanistic behavior.

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