Computational Design of Transition Metal Catalysts for Hydrodefluorination of Trifluoromethylarenes using Hydrosilane

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{
  "metadata": {
    "edited_by": 98, 
    "owner": 1375, 
    "_oai": {
      "id": "oai:materialscloud.org:2197"
    }, 
    "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.", 
    "mcid": "2024.88", 
    "id": "2197", 
    "license": "Creative Commons Attribution 4.0 International", 
    "license_addendum": null, 
    "references": [
      {
        "citation": "T. Worakul, B. Sawatlon, P. Surawatanawong, submitted (2024)", 
        "type": "Journal reference", 
        "doi": ""
      }
    ], 
    "doi": "10.24435/materialscloud:h6-fj", 
    "keywords": [
      "volcano plot", 
      "catalysis", 
      "carbenes", 
      "electronic structure"
    ], 
    "contributors": [
      {
        "affiliations": [
          "Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400, Thailand"
        ], 
        "familyname": "Worakul", 
        "email": "thanapat.worakul@epfl.ch", 
        "givennames": "Thanapat"
      }, 
      {
        "affiliations": [
          "Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand"
        ], 
        "familyname": "Sawatlon", 
        "email": "Boodsarin.s@chula.ac.th", 
        "givennames": "Boodsarin"
      }, 
      {
        "affiliations": [
          "Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Mahidol University, Bangkok 10400, Thailand", 
          "Center of Sustainable Energy and Green Materials, Mahidol University, Salaya, Nakhon Pathom 73170, Thailand"
        ], 
        "familyname": "Surawatanawong", 
        "email": "panida.sur@mahidol.ac.th", 
        "givennames": "Panida"
      }
    ], 
    "conceptrecid": "2196", 
    "version": 1, 
    "publication_date": "Jun 14, 2024, 14:50:48", 
    "is_last": true, 
    "status": "published", 
    "_files": [
      {
        "size": 651730, 
        "checksum": "md5:a00e078ed4d5b5383d2a64f790a69f65", 
        "description": "ZIP file containing optimized XYZ structures of ground-state species and transition states", 
        "key": "geom.zip"
      }, 
      {
        "size": 13198, 
        "checksum": "md5:4895cb3b346b420d65e2d7c0b300c18a", 
        "description": "XLSX file containing energy profile of the catalytic reaction under [[NiL2]2(COD)] reference state without CsF additive", 
        "key": "REF1.xlsx"
      }, 
      {
        "size": 10254, 
        "checksum": "md5:cac3d482715527b6c68406f991945814", 
        "description": "XLSX file containing energy profile of the catalytic reaction under [[NiL2]2(COD)] reference state with CsF additive", 
        "key": "REF1_CsF.xlsx"
      }, 
      {
        "size": 13219, 
        "checksum": "md5:171effd9d243fa05b2b4a129c2c6cf61", 
        "description": "XLSX file containing energy profile of the catalytic reaction under NiL2 reference state without CsF additive", 
        "key": "REF2.xlsx"
      }, 
      {
        "size": 1695, 
        "checksum": "md5:f7a156f49ab55a709a591ca4f270f1b7", 
        "description": "CSV file containing electronic and steric descriptors for ligands", 
        "key": "nico3L_nbo_feature.csv"
      }, 
      {
        "size": 959, 
        "checksum": "md5:0c10a1111ba8b9714fd68e0b2cbc45e9", 
        "description": "ZIP file containing input examples of Gaussian16 calculations", 
        "key": "g16_inp.zip"
      }
    ], 
    "title": "Computational Design of Transition Metal Catalysts for Hydrodefluorination of Trifluoromethylarenes using Hydrosilane"
  }, 
  "id": "2197", 
  "updated": "2024-06-14T12:50:48.095035+00:00", 
  "created": "2024-05-22T18:54:45.536706+00:00", 
  "revision": 13
}