New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry

Photolysis products of dichloroacetyl chloride (DCAC) isolated in Ar matrix and in gas phase, in the absence and presence of molecular oxygen, were studied by means of FTIR spectroscopy. The samples were exposed to light of different energy ranges (200-800, 280-320, 350-450 and 400-800 nm). DCAC is...

Descripción completa

Detalles Bibliográficos
Autores principales: Tamone, Luciana Mariel, Picone, Andrea Lorena, Romano, Rosana Mariel
Formato: Articulo
Lenguaje:Inglés
Publicado: 2021
Materias:
Química
Dichloroacetyl chloride
Matrix-isolation
Photochemistry
IR spectroscopy
Dimers
Acceso en línea:http://sedici.unlp.edu.ar/handle/10915/112819
Aporte de:
SEDICI (UNLP) de Universidad Nacional de La Plata
id I19-R120-10915-112819
record_format dspace
institution Universidad Nacional de La Plata
institution_str I-19
repository_str R-120
collection SEDICI (UNLP)
language Inglés
topic Química
Dichloroacetyl chloride
Matrix-isolation
Photochemistry
IR spectroscopy
Dimers
spellingShingle Química
Dichloroacetyl chloride
Matrix-isolation
Photochemistry
IR spectroscopy
Dimers
Tamone, Luciana Mariel
Picone, Andrea Lorena
Romano, Rosana Mariel
New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry
topic_facet Química
Dichloroacetyl chloride
Matrix-isolation
Photochemistry
IR spectroscopy
Dimers
description Photolysis products of dichloroacetyl chloride (DCAC) isolated in Ar matrix and in gas phase, in the absence and presence of molecular oxygen, were studied by means of FTIR spectroscopy. The samples were exposed to light of different energy ranges (200-800, 280-320, 350-450 and 400-800 nm). DCAC is photostable when irradiated with light of wavelengths above 400 nm, and gives dichloroketene after photolysis with light between 280-320 and 350-450 nm. Exposure of DCAC to broad-band radiation (200-800 nm) produces dichloroketene as an intermediate photoproduct, and different 1:1 CHCl3:CO molecular complexes after further irradiation. HCl, CO and CHCl3 were detected in gas-phase DCAC photolysis. ClC(O)CCl2CCl2H molecule was also proposed, in a mechanism that involve the insertion of :CCl2 biradical into the CC bond of DCAC. The photochemical reaction of DCAC with O2 in Ar matrix gives Cl2CO and CO2. The same photoproducts, together with HCl, were observed in the gas-phase photochemical reaction. Additionally, the FTIR spectra of DCAC isolated in solid Ar were fully interpreted in terms of an equilibrium between syn (the HC bond syn with respect to the CO bond) and gauche conformers. Some absorptions, which grow as the DCAC:Ar ratio increases, were attributed to dimeric forms. The most stable dimer was predicted by DFT calculations as composed by two DCAC molecules with syn conformations, interacting through two H-bonds in a structure with Ci symmetry.
format Articulo
Articulo
author Tamone, Luciana Mariel
Picone, Andrea Lorena
Romano, Rosana Mariel
author_facet Tamone, Luciana Mariel
Picone, Andrea Lorena
Romano, Rosana Mariel
author_sort Tamone, Luciana Mariel
title New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry
title_short New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry
title_full New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry
title_fullStr New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry
title_full_unstemmed New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry
title_sort new insights into the ar-matrix-isolation ftir spectroscopy and photochemistry of dichloroacetyl chloride, clc(o)chcl<sub>2</sub>: influence of o<sub>2</sub> and comparison with gas-phase photochemistry
publishDate 2021
url http://sedici.unlp.edu.ar/handle/10915/112819
work_keys_str_mv AT tamonelucianamariel newinsightsintothearmatrixisolationftirspectroscopyandphotochemistryofdichloroacetylchlorideclcochclsub2subinfluenceofosub2subandcomparisonwithgasphasephotochemistry
AT piconeandrealorena newinsightsintothearmatrixisolationftirspectroscopyandphotochemistryofdichloroacetylchlorideclcochclsub2subinfluenceofosub2subandcomparisonwithgasphasephotochemistry
AT romanorosanamariel newinsightsintothearmatrixisolationftirspectroscopyandphotochemistryofdichloroacetylchlorideclcochclsub2subinfluenceofosub2subandcomparisonwithgasphasephotochemistry
bdutipo_str Repositorios
_version_ 1764820445918396416

Ejemplares similares