Homolytic S–Cl bond dissociation enthalpies of sulfenyl chlorides – a high-level G4 thermochemical study

Robert O Reilly John Christopher, Mannix Balanay Padayhag

Research output: Contribution to journalArticle

  • 1 Citations

Abstract

Numerous reactions between sulfenyl chlorides and organic molecules proceed by way of radical reactions, in which homolytic cleavage of the S–Cl bond is a key step. Owing to the lack of data concerning the quantitative effect of substituents in governing the strength of S–Cl bonds toward homolytic cleavage, the present article reports an extensive dataset of gas-phase S–Cl bond dissociation enthalpies (BDEs) obtained using the high-level G4 thermochemical protocol. The BDEs of the species in this set range from 207.2 (ONSCl) to 279.7 kJ mol−1 (tBuSCl), with HSCl having a BDE of 267.6 kJ mol−1. In addition, the gas-phase S–Cl BDEs of six sulfonyl chlorides have also been reported, and these range from 267.2 kJ mol–1 (CF3SO2Cl) to 283.0 kJ mol−1 (FSO2Cl).

LanguageEnglish
Article number100180
JournalChemical Data Collections
Volume19
DOIs
Publication statusPublished - Feb 1 2019

Fingerprint

Chlorides
Enthalpy
Gases
Molecules

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Homolytic S–Cl bond dissociation enthalpies of sulfenyl chlorides – a high-level G4 thermochemical study. / O Reilly John Christopher, Robert; Balanay Padayhag, Mannix.

In: Chemical Data Collections, Vol. 19, 100180, 01.02.2019.

Research output: Contribution to journalArticle

@article{5c2d6180b96d4c19b5eea757487025bd,
title = "Homolytic S–Cl bond dissociation enthalpies of sulfenyl chlorides – a high-level G4 thermochemical study",
abstract = "Numerous reactions between sulfenyl chlorides and organic molecules proceed by way of radical reactions, in which homolytic cleavage of the S–Cl bond is a key step. Owing to the lack of data concerning the quantitative effect of substituents in governing the strength of S–Cl bonds toward homolytic cleavage, the present article reports an extensive dataset of gas-phase S–Cl bond dissociation enthalpies (BDEs) obtained using the high-level G4 thermochemical protocol. The BDEs of the species in this set range from 207.2 (ONSCl) to 279.7 kJ mol−1 (tBuSCl), with HSCl having a BDE of 267.6 kJ mol−1. In addition, the gas-phase S–Cl BDEs of six sulfonyl chlorides have also been reported, and these range from 267.2 kJ mol–1 (CF3SO2Cl) to 283.0 kJ mol−1 (FSO2Cl).",
author = "{O Reilly John Christopher}, Robert and {Balanay Padayhag}, Mannix",
year = "2019",
month = "2",
day = "1",
doi = "10.1016/j.cdc.2019.100180",
language = "English",
volume = "19",
journal = "Chemical Data Collections",
issn = "2405-8300",
publisher = "Elsevier",

}

TY - JOUR

T1 - Homolytic S–Cl bond dissociation enthalpies of sulfenyl chlorides – a high-level G4 thermochemical study

AU - O Reilly John Christopher, Robert

AU - Balanay Padayhag, Mannix

PY - 2019/2/1

Y1 - 2019/2/1

N2 - Numerous reactions between sulfenyl chlorides and organic molecules proceed by way of radical reactions, in which homolytic cleavage of the S–Cl bond is a key step. Owing to the lack of data concerning the quantitative effect of substituents in governing the strength of S–Cl bonds toward homolytic cleavage, the present article reports an extensive dataset of gas-phase S–Cl bond dissociation enthalpies (BDEs) obtained using the high-level G4 thermochemical protocol. The BDEs of the species in this set range from 207.2 (ONSCl) to 279.7 kJ mol−1 (tBuSCl), with HSCl having a BDE of 267.6 kJ mol−1. In addition, the gas-phase S–Cl BDEs of six sulfonyl chlorides have also been reported, and these range from 267.2 kJ mol–1 (CF3SO2Cl) to 283.0 kJ mol−1 (FSO2Cl).

AB - Numerous reactions between sulfenyl chlorides and organic molecules proceed by way of radical reactions, in which homolytic cleavage of the S–Cl bond is a key step. Owing to the lack of data concerning the quantitative effect of substituents in governing the strength of S–Cl bonds toward homolytic cleavage, the present article reports an extensive dataset of gas-phase S–Cl bond dissociation enthalpies (BDEs) obtained using the high-level G4 thermochemical protocol. The BDEs of the species in this set range from 207.2 (ONSCl) to 279.7 kJ mol−1 (tBuSCl), with HSCl having a BDE of 267.6 kJ mol−1. In addition, the gas-phase S–Cl BDEs of six sulfonyl chlorides have also been reported, and these range from 267.2 kJ mol–1 (CF3SO2Cl) to 283.0 kJ mol−1 (FSO2Cl).

UR - http://www.scopus.com/inward/record.url?scp=85059861698&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85059861698&partnerID=8YFLogxK

U2 - 10.1016/j.cdc.2019.100180

DO - 10.1016/j.cdc.2019.100180

M3 - Article

VL - 19

JO - Chemical Data Collections

T2 - Chemical Data Collections

JF - Chemical Data Collections

SN - 2405-8300

M1 - 100180

ER -