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Can a gas phase contact ion pair containing a hydrocarbon carbocation be formed in the ground state?

So far, no conclusive evidence of a ground-state contact ion-pair containing a hydrocarbon carbocation has been given in the gas phase. Due to the very high stability of the 1,2:4,5-dibenzotropylium (or dibenzo[a,d]tropylium) carbocation, we suggest (supported by DFT and MP2 calculations) the format...

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Autores principales: Araújo, José R., de Andrade, Railton B., Batista, Hélcio J., Ventura, Elizete, do Monte, Silmar A.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8694316/
https://www.ncbi.nlm.nih.gov/pubmed/35424376
http://dx.doi.org/10.1039/d0ra10523f
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author Araújo, José R.
de Andrade, Railton B.
Batista, Hélcio J.
Ventura, Elizete
do Monte, Silmar A.
author_facet Araújo, José R.
de Andrade, Railton B.
Batista, Hélcio J.
Ventura, Elizete
do Monte, Silmar A.
author_sort Araújo, José R.
collection PubMed
description So far, no conclusive evidence of a ground-state contact ion-pair containing a hydrocarbon carbocation has been given in the gas phase. Due to the very high stability of the 1,2:4,5-dibenzotropylium (or dibenzo[a,d]tropylium) carbocation, we suggest (supported by DFT and MP2 calculations) the formation of a contact ion pair between this carbocation and chloride, occurring during the reaction between 1,2:4,5-dibenzotropyl (also named dibenzo[a,d]tropyl or dibenzo[a,d]cycloheptenyl) radical and chlorine atom at very low temperatures, through the harpoon mechanism. This is the first modeling study to find computational evidence for the possibility of a gas-phase contact ion pair (containing a hydrocarbon carbocation) formed in the ground state. Identification of this metastable species can be carried out by trapping it in He nanodroplets, along with infrared laser spectroscopy routinely coupled with this technique.
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spelling pubmed-86943162022-04-13 Can a gas phase contact ion pair containing a hydrocarbon carbocation be formed in the ground state? Araújo, José R. de Andrade, Railton B. Batista, Hélcio J. Ventura, Elizete do Monte, Silmar A. RSC Adv Chemistry So far, no conclusive evidence of a ground-state contact ion-pair containing a hydrocarbon carbocation has been given in the gas phase. Due to the very high stability of the 1,2:4,5-dibenzotropylium (or dibenzo[a,d]tropylium) carbocation, we suggest (supported by DFT and MP2 calculations) the formation of a contact ion pair between this carbocation and chloride, occurring during the reaction between 1,2:4,5-dibenzotropyl (also named dibenzo[a,d]tropyl or dibenzo[a,d]cycloheptenyl) radical and chlorine atom at very low temperatures, through the harpoon mechanism. This is the first modeling study to find computational evidence for the possibility of a gas-phase contact ion pair (containing a hydrocarbon carbocation) formed in the ground state. Identification of this metastable species can be carried out by trapping it in He nanodroplets, along with infrared laser spectroscopy routinely coupled with this technique. The Royal Society of Chemistry 2021-01-20 /pmc/articles/PMC8694316/ /pubmed/35424376 http://dx.doi.org/10.1039/d0ra10523f Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Araújo, José R.
de Andrade, Railton B.
Batista, Hélcio J.
Ventura, Elizete
do Monte, Silmar A.
Can a gas phase contact ion pair containing a hydrocarbon carbocation be formed in the ground state?
title Can a gas phase contact ion pair containing a hydrocarbon carbocation be formed in the ground state?
title_full Can a gas phase contact ion pair containing a hydrocarbon carbocation be formed in the ground state?
title_fullStr Can a gas phase contact ion pair containing a hydrocarbon carbocation be formed in the ground state?
title_full_unstemmed Can a gas phase contact ion pair containing a hydrocarbon carbocation be formed in the ground state?
title_short Can a gas phase contact ion pair containing a hydrocarbon carbocation be formed in the ground state?
title_sort can a gas phase contact ion pair containing a hydrocarbon carbocation be formed in the ground state?
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8694316/
https://www.ncbi.nlm.nih.gov/pubmed/35424376
http://dx.doi.org/10.1039/d0ra10523f
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