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 | |
| Publication status | Published - Apr 1 2019 |
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Keywords
- Bond dissociation energies
- DFT
- Fluoride
- Sulfenyl
- W1w
ASJC Scopus subject areas
- Chemistry(all)
Cite this
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
}
TY - JOUR
T1 - 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
AU - O Reilly John Christopher, Robert
AU - Balanay Padayhag, Mannix
PY - 2019/4/1
Y1 - 2019/4/1
N2 - 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.
AB - 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.
KW - Bond dissociation energies
KW - DFT
KW - Fluoride
KW - Sulfenyl
KW - W1w
UR - http://www.scopus.com/inward/record.url?scp=85061052736&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85061052736&partnerID=8YFLogxK
U2 - 10.1016/j.cdc.2019.100186
DO - 10.1016/j.cdc.2019.100186
M3 - Article
VL - 20
JO - Chemical Data Collections
JF - Chemical Data Collections
SN - 2405-8300
M1 - 100186
ER -