Thanapat Worakul^1*, Boodsarin Sawatlon^2*, Panida Surawatanawong^1,3*

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

* Corresponding authors emails: thanapat.worakul@epfl.ch, Boodsarin.s@chula.ac.th, panida.sur@mahidol.ac.th

DOI10.24435/materialscloud:h6-fj [version v1]

Publication date: Jun 14, 2024

How to cite this record

Thanapat Worakul, Boodsarin Sawatlon, Panida Surawatanawong, Computational Design of Transition Metal Catalysts for Hydrodefluorination of Trifluoromethylarenes using Hydrosilane, Materials Cloud Archive 2024.88 (2024), https://doi.org/10.24435/materialscloud:h6-fj

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.

Materials Cloud sections using this data

Files

File name	Size	Description
geom.zip MD5md5:a00e078ed4d5b5383d2a64f790a69f65	636.5 KiB	ZIP file containing optimized XYZ structures of ground-state species and transition states
REF1.xlsx MD5md5:4895cb3b346b420d65e2d7c0b300c18a	12.9 KiB	XLSX file containing energy profile of the catalytic reaction under [[NiL2]2(COD)] reference state without CsF additive
REF1_CsF.xlsx MD5md5:cac3d482715527b6c68406f991945814	10.0 KiB	XLSX file containing energy profile of the catalytic reaction under [[NiL2]2(COD)] reference state with CsF additive
REF2.xlsx MD5md5:171effd9d243fa05b2b4a129c2c6cf61	12.9 KiB	XLSX file containing energy profile of the catalytic reaction under NiL2 reference state without CsF additive
nico3L_nbo_feature.csv MD5md5:f7a156f49ab55a709a591ca4f270f1b7	1.7 KiB	CSV file containing electronic and steric descriptors for ligands
g16_inp.zip MD5md5:0c10a1111ba8b9714fd68e0b2cbc45e9	959 Bytes	ZIP file containing input examples of Gaussian16 calculations

License

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External references

Keywords

volcano plot catalysis carbenes electronic structure