Zhu, Shuaiwei; O'Reilly, Robert

Author(s)

Zhu, Shuaiwei

O'Reilly, Robert

Publication Date

2020

Abstract

This study reports the gas-phase homolytic S–Br bond dissociation enthalpies (at 298 K) for a set of 44 sulfenyl bromide derivatives (RSBr) obtained using the high-level G4 thermochemical protocol. For the species in this set, we find that the BDEs range from 178.0 kJ mol–1 (F3CSSBr) to 239.5 kJ mol–1 (HC(=NH)SBr). We have additionally reported molecule and radical stabilization enthalpies for all species, allowing for insights to be gained as to the effect of substituents in both the sulfenyl bromide reactants and the sulfur-centered radical products. In addition, we have also reported the BDEs of six sufinyl bromides (RS(=O)Br) and six sulfonyl bromides (RSO2Br). For the sulfinyl bromides, the BDEs range from 156.6 kJ mol–1 (F3CS(=O)Br) to 173.8 kJ mol–1 (tBuS(=O)Br), whilst for the sulfonyl bromides, the BDEs range from 211.0 kJ mol–1 (F3CSO2Br) to 226.2 kJ mol–1 (FSO2Br).

Citation

Chemical Data Collections, v.28

ISSN

2405-8300

Link

https://hdl.handle.net/1959.11/58212

Publisher

Elsevier BV

Title

A quantum chemical study of the gas-phase homolytic S–Br bond dissociation enthalpies of sulfenyl bromides

Type of document

Journal Article

Entity Type

Publication

Author(s)	Zhu, Shuaiwei O'Reilly, Robert
Publication Date	2020
Abstract	This study reports the gas-phase homolytic S–Br bond dissociation enthalpies (at 298 K) for a set of 44 sulfenyl bromide derivatives (RSBr) obtained using the high-level G4 thermochemical protocol. For the species in this set, we find that the BDEs range from 178.0 kJ mol<sup>–1</sup> (F3CSSBr) to 239.5 kJ mol<sup>–1</sup> (HC(=NH)SBr). We have additionally reported molecule and radical stabilization enthalpies for all species, allowing for insights to be gained as to the effect of substituents in both the sulfenyl bromide reactants and the sulfur-centered radical products. In addition, we have also reported the BDEs of six sufinyl bromides (RS(=O)Br) and six sulfonyl bromides (RSO<sub>2</sub>Br). For the sulfinyl bromides, the BDEs range from 156.6 kJ mol<sup>–1</sup> (F<sub>3</sub>CS(=O)Br) to 173.8 kJ mol<sup>–1</sup> (<sup>t</sup>BuS(=O)Br), whilst for the sulfonyl bromides, the BDEs range from 211.0 kJ mol<sup>–1</sup> (F3CSO2Br) to 226.2 kJ mol<sup>–1</sup> (FSO<sub>2</sub>Br).
Citation	Chemical Data Collections, v.28
ISSN	2405-8300
Link	https://hdl.handle.net/1959.11/58212
Publisher	Elsevier BV
Title	A quantum chemical study of the gas-phase homolytic S–Br bond dissociation enthalpies of sulfenyl bromides
Type of document	Journal Article
Entity Type	Publication

A quantum chemical study of the gas-phase homolytic S–Br bond dissociation enthalpies of sulfenyl bromides

Files: