| Author(s) |
O'Reilly, Robert
Balanay, Mannix P
|
| Publication Date |
2019
|
| Abstract |
<p>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 298K) for the species in this set range from 316.2 (HCCSF) to 368.1 (H<sub>2</sub>CCHSF) kJ mol<sup>–1</sup>. We additionally report fluorine-transfer energies (FTEs), corresponding to the energetics of fluorine transfer from RSF to H<sub>2</sub>S. At 298K, the FTEs range from –10.7 (H<sub>2</sub>AlSF) to 90.7 (MeHNSF) kJ mol<sup>–1</sup>. 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 1.6kJ mol<sup>–1</sup>, whilst for the FTEs, B2K-PLYP and DSD-PBEP86 offer the best performance with MADs of 0.5kJ mol<sup>–1</sup>.</p>
|
| Citation |
Chemical Data Collections, v.20
|
| ISSN |
2405-8300
|
| Link | |
| Publisher |
Elsevier BV
|
| 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
|
| Type of document |
Journal Article
|
| Entity Type |
Publication
|
| Name | Size | format | Description | Link |
|---|