Unstable chloronitrile oxide, ClCNO, and its stable ring dimer: Generation, spectroscopy, and structure

T. Pasinszki, Nicholas P C Westwood

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

The unstable chloronitrile oxide molecule ClCNO has been generated from dichloroformaldoxime Cl2C=NOH by low-pressure gas-phase thermolysis or by a gas-solid reaction with HgO or metals. ClCNO is characterized in the gas phase by mid-infrared and HeI photoelectron spectroscopy, with the ground-state geometry obtained from ab initio calculations at the B3-LYP, MPn (n = 2-4), QCISD, QCISD(T), CCSD, and CCSD(T) levels using basis sets ranging from 6-31G** through 6-311G(2d) to cc-pVTZ. The calculated structure is strongly dependent upon the method employed and on basis set size, but is predicted to be linear or quasi-linear. The stable ring dimer, dichlorofuroxan, separately synthesized, does not yield the monomer upon thermolysis but leads to ClC(O)CN as a major product. The ring dimer has been investigated in the gas phase by infrared, photoelectron, and photoionization mass spectroscopy and also by ab initio calculations at the B3-LYP/6-31G** level. The same level of theory was applied to an investigation of the mechanism by which ClCNO dimerizes, this being found to be a typical two-step process; the first being formation of the C-C bond and the second the formation of the N-O bond with ring closure.

Original languageEnglish
Pages (from-to)4939-4947
Number of pages9
JournalJournal of Physical Chemistry A
Volume102
Issue number25
Publication statusPublished - Jun 18 1998

Fingerprint

Dimers
Oxides
Gases
dimers
Spectroscopy
vapor phases
Thermolysis
oxides
rings
spectroscopy
Infrared radiation
Photoionization
closures
photoionization
photoelectrons
mass spectroscopy
Photoelectron spectroscopy
low pressure
Photoelectrons
monomers

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Unstable chloronitrile oxide, ClCNO, and its stable ring dimer : Generation, spectroscopy, and structure. / Pasinszki, T.; Westwood, Nicholas P C.

In: Journal of Physical Chemistry A, Vol. 102, No. 25, 18.06.1998, p. 4939-4947.

Research output: Contribution to journalArticle

@article{c0addb08b25343b293cd9cc04638189b,
title = "Unstable chloronitrile oxide, ClCNO, and its stable ring dimer: Generation, spectroscopy, and structure",
abstract = "The unstable chloronitrile oxide molecule ClCNO has been generated from dichloroformaldoxime Cl2C=NOH by low-pressure gas-phase thermolysis or by a gas-solid reaction with HgO or metals. ClCNO is characterized in the gas phase by mid-infrared and HeI photoelectron spectroscopy, with the ground-state geometry obtained from ab initio calculations at the B3-LYP, MPn (n = 2-4), QCISD, QCISD(T), CCSD, and CCSD(T) levels using basis sets ranging from 6-31G** through 6-311G(2d) to cc-pVTZ. The calculated structure is strongly dependent upon the method employed and on basis set size, but is predicted to be linear or quasi-linear. The stable ring dimer, dichlorofuroxan, separately synthesized, does not yield the monomer upon thermolysis but leads to ClC(O)CN as a major product. The ring dimer has been investigated in the gas phase by infrared, photoelectron, and photoionization mass spectroscopy and also by ab initio calculations at the B3-LYP/6-31G** level. The same level of theory was applied to an investigation of the mechanism by which ClCNO dimerizes, this being found to be a typical two-step process; the first being formation of the C-C bond and the second the formation of the N-O bond with ring closure.",
author = "T. Pasinszki and Westwood, {Nicholas P C}",
year = "1998",
month = "6",
day = "18",
language = "English",
volume = "102",
pages = "4939--4947",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "25",

}

TY - JOUR

T1 - Unstable chloronitrile oxide, ClCNO, and its stable ring dimer

T2 - Generation, spectroscopy, and structure

AU - Pasinszki, T.

AU - Westwood, Nicholas P C

PY - 1998/6/18

Y1 - 1998/6/18

N2 - The unstable chloronitrile oxide molecule ClCNO has been generated from dichloroformaldoxime Cl2C=NOH by low-pressure gas-phase thermolysis or by a gas-solid reaction with HgO or metals. ClCNO is characterized in the gas phase by mid-infrared and HeI photoelectron spectroscopy, with the ground-state geometry obtained from ab initio calculations at the B3-LYP, MPn (n = 2-4), QCISD, QCISD(T), CCSD, and CCSD(T) levels using basis sets ranging from 6-31G** through 6-311G(2d) to cc-pVTZ. The calculated structure is strongly dependent upon the method employed and on basis set size, but is predicted to be linear or quasi-linear. The stable ring dimer, dichlorofuroxan, separately synthesized, does not yield the monomer upon thermolysis but leads to ClC(O)CN as a major product. The ring dimer has been investigated in the gas phase by infrared, photoelectron, and photoionization mass spectroscopy and also by ab initio calculations at the B3-LYP/6-31G** level. The same level of theory was applied to an investigation of the mechanism by which ClCNO dimerizes, this being found to be a typical two-step process; the first being formation of the C-C bond and the second the formation of the N-O bond with ring closure.

AB - The unstable chloronitrile oxide molecule ClCNO has been generated from dichloroformaldoxime Cl2C=NOH by low-pressure gas-phase thermolysis or by a gas-solid reaction with HgO or metals. ClCNO is characterized in the gas phase by mid-infrared and HeI photoelectron spectroscopy, with the ground-state geometry obtained from ab initio calculations at the B3-LYP, MPn (n = 2-4), QCISD, QCISD(T), CCSD, and CCSD(T) levels using basis sets ranging from 6-31G** through 6-311G(2d) to cc-pVTZ. The calculated structure is strongly dependent upon the method employed and on basis set size, but is predicted to be linear or quasi-linear. The stable ring dimer, dichlorofuroxan, separately synthesized, does not yield the monomer upon thermolysis but leads to ClC(O)CN as a major product. The ring dimer has been investigated in the gas phase by infrared, photoelectron, and photoionization mass spectroscopy and also by ab initio calculations at the B3-LYP/6-31G** level. The same level of theory was applied to an investigation of the mechanism by which ClCNO dimerizes, this being found to be a typical two-step process; the first being formation of the C-C bond and the second the formation of the N-O bond with ring closure.

UR - http://www.scopus.com/inward/record.url?scp=0000451774&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000451774&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0000451774

VL - 102

SP - 4939

EP - 4947

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 25

ER -