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

doi:10.1016/j.cdc.2019.100186

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

Department of Chemistry

Research output: Contribution to journal › Article

1 Citation (Scopus)

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 language	English
Article number	100186
Journal	Chemical Data Collections
Volume	20
DOIs	https://doi.org/10.1016/j.cdc.2019.100186
Publication status	Published - 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

O Reilly John Christopher, R., & Balanay Padayhag, M. (2019). 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. Chemical Data Collections, 20, [100186]. https://doi.org/10.1016/j.cdc.2019.100186

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. / O Reilly John Christopher, Robert; Balanay Padayhag, Mannix.

In: Chemical Data Collections, Vol. 20, 100186, 01.04.2019.

Research output: Contribution to journal › Article

O Reilly John Christopher, R & Balanay Padayhag, M 2019, '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', Chemical Data Collections, vol. 20, 100186. https://doi.org/10.1016/j.cdc.2019.100186

O Reilly John Christopher R, Balanay Padayhag M. 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. Chemical Data Collections. 2019 Apr 1;20. 100186. https://doi.org/10.1016/j.cdc.2019.100186

O Reilly John Christopher, Robert ; Balanay Padayhag, Mannix. / 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. In: Chemical Data Collections. 2019 ; Vol. 20.

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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.",

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10.1016/j.cdc.2019.100186