Published June 14, 2024 | Version v1
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Computational Design of Transition Metal Catalysts for Hydrodefluorination of Trifluoromethylarenes using Hydrosilane

  • 1. Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400, Thailand
  • 2. Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand
  • 3. Center of Sustainable Energy and Green Materials, Mahidol University, Salaya, Nakhon Pathom 73170, Thailand

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Description

The C-F activation is one of the important processes in chemical synthesis. Here, we studied the hydrodefluorination of PhCF3 with SiMe2Ph-H catalyzed by Ni(0) complexes. The mechanisms involve three main steps: C-F bond cleavage of PhCF3 on the nickel complex, transmetalation of Ni-F with SiMe2Ph-H to form a nickel hydride complex, and C-H reductive elimination of PhCF2H. We performed density functional calculations on nickel complexes with thirty carbene and phosphine ligands to obtain the relative free energy profiles. Then, linear free energy scaling relationships were determined and molecular volcano plots were constructed. To accurately describe catalytic activity, we found that multiple reference states must be considered. Thus, the concept of "reference-generalized volcano plots (RGVPs)" was introduced to assist with the selection of the appropriate reference state to determine catalytic activity. Our regression models indicate that electronic properties of ligands significantly influence energy descriptors more than steric size, although steric hindrance affects reference state stability. Optimal ligands are highly electron-donating with small-to-moderate steric sizes. This study highlights the importance of selecting appropriate ligands and metal centers to optimize catalytic activity. Examples of input files for density functional calculations in Gaussian16 to obtain relative free energies for all intermediates and transition states, the spreadsheet tables including the calculated relative free energies for generating LFESRs and volcano plots, and all optimized Cartesian coordinates are provided.

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References

Journal reference
T. Worakul, B. Sawatlon, P. Surawatanawong, submitted (2024)