A quantum chemical study of the effect of substituents in governing the strength of the S–F bonds of sulfenyl-type fluorides toward homolytic dissociation and fluorine atom transfer

Robert O Reilly John Christopher, Mannix Balanay Padayhag

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Abstract

The gas-phase homolytic S–F bond dissociation energies (BDEs) of 21 sulfenyl-type fluorides (RSF) have been obtained using the W1w thermochemical protocol. The BDEs (at 298 K) for the species in this set range from 316.2 (HCCSF) to 368.1 (H2CCHSF) kJ mol–1. We additionally report fluorine-transfer energies (FTEs), corresponding to the energetics of fluorine transfer from RSF to H2S. At 298 K, the FTEs range from –10.7 (H2AlSF) to 90.7 (MeHNSF) kJ mol–1. We have also assessed the performance of a wide range of density functional theory (DFT) and double-hybrid DFT methods (in conjunction with the A'VQZ basis set) for the calculation of these quantities. For the calculation of S–F BDEs, the M06-2X procedure offers the best performance, with a mean absolute deviation (MAD) of 1.6 kJ mol–1, whilst for the FTEs, B2K-PLYP and DSD-PBEP86 offer the best performance with MADs of 0.5 kJ mol–1.

Original languageEnglish
Article number100186
JournalChemical Data Collections
Volume20
DOIs
Publication statusPublished - Apr 1 2019

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Fluorine
Fluorides
Energy transfer
Atoms
Density functional theory
Gases

Keywords

  • Bond dissociation energies
  • DFT
  • Fluoride
  • Sulfenyl
  • W1w

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "A quantum chemical study of the effect of substituents in governing the strength of the S–F bonds of sulfenyl-type fluorides toward homolytic dissociation and fluorine atom transfer",
abstract = "The gas-phase homolytic S–F bond dissociation energies (BDEs) of 21 sulfenyl-type fluorides (RSF) have been obtained using the W1w thermochemical protocol. The BDEs (at 298 K) for the species in this set range from 316.2 (HCCSF) to 368.1 (H2CCHSF) kJ mol–1. We additionally report fluorine-transfer energies (FTEs), corresponding to the energetics of fluorine transfer from RSF to H2S. At 298 K, the FTEs range from –10.7 (H2AlSF) to 90.7 (MeHNSF) kJ mol–1. We have also assessed the performance of a wide range of density functional theory (DFT) and double-hybrid DFT methods (in conjunction with the A'VQZ basis set) for the calculation of these quantities. For the calculation of S–F BDEs, the M06-2X procedure offers the best performance, with a mean absolute deviation (MAD) of 1.6 kJ mol–1, whilst for the FTEs, B2K-PLYP and DSD-PBEP86 offer the best performance with MADs of 0.5 kJ mol–1.",
keywords = "Bond dissociation energies, DFT, Fluoride, Sulfenyl, W1w",
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