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Why Can Cationic Halogen Bond Donors Activate the Ritter-Type Solvolysis of Benzhydryl Bromide but Cationic Hydrogen Bond Donors Can Not?

[Image: see text] It is found by experiment that the cationic halogen bond donors (cationic iodoimidazolium compounds) can activate the Ritter-type solvolysis of benzhydryl bromide, while the cationic hydrogen bond donors (cationic imidazolium compounds) could not. To understand the activation mecha...

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Autores principales: Wang, Yueyan, Su, Peifeng
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2020
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7469379/
https://www.ncbi.nlm.nih.gov/pubmed/32905280
http://dx.doi.org/10.1021/acsomega.0c03000
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author Wang, Yueyan
Su, Peifeng
author_facet Wang, Yueyan
Su, Peifeng
author_sort Wang, Yueyan
collection PubMed
description [Image: see text] It is found by experiment that the cationic halogen bond donors (cationic iodoimidazolium compounds) can activate the Ritter-type solvolysis of benzhydryl bromide, while the cationic hydrogen bond donors (cationic imidazolium compounds) could not. To understand the activation mechanism, various noncovalent interactions between benzhydryl bromide and a series of activators in solution, including halogen bond, hydrogen bond, lone pair···π/π(+), and C–H···π/π(+), were explored theoretically. Our study revealed that the activation difference can be contributed by the variation of the noncovalent interactions. For halogen bond donors, the successful activation is attributed by halogen bond and lone pair···π. The halogen bonds mainly provide the stabilization energy of the ion-pair complex with the help of lone pair···π. For hydrogen-bond donors, the contribution of the hydrogen bond is unable to compensate the like-charge repulsion arising from the generation of the carbocation, leading to the unsuccessful activation. In general, lone pair···π makes a difference.
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spelling pubmed-74693792020-09-04 Why Can Cationic Halogen Bond Donors Activate the Ritter-Type Solvolysis of Benzhydryl Bromide but Cationic Hydrogen Bond Donors Can Not? Wang, Yueyan Su, Peifeng ACS Omega [Image: see text] It is found by experiment that the cationic halogen bond donors (cationic iodoimidazolium compounds) can activate the Ritter-type solvolysis of benzhydryl bromide, while the cationic hydrogen bond donors (cationic imidazolium compounds) could not. To understand the activation mechanism, various noncovalent interactions between benzhydryl bromide and a series of activators in solution, including halogen bond, hydrogen bond, lone pair···π/π(+), and C–H···π/π(+), were explored theoretically. Our study revealed that the activation difference can be contributed by the variation of the noncovalent interactions. For halogen bond donors, the successful activation is attributed by halogen bond and lone pair···π. The halogen bonds mainly provide the stabilization energy of the ion-pair complex with the help of lone pair···π. For hydrogen-bond donors, the contribution of the hydrogen bond is unable to compensate the like-charge repulsion arising from the generation of the carbocation, leading to the unsuccessful activation. In general, lone pair···π makes a difference. American Chemical Society 2020-08-24 /pmc/articles/PMC7469379/ /pubmed/32905280 http://dx.doi.org/10.1021/acsomega.0c03000 Text en Copyright © 2020 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle Wang, Yueyan
Su, Peifeng
Why Can Cationic Halogen Bond Donors Activate the Ritter-Type Solvolysis of Benzhydryl Bromide but Cationic Hydrogen Bond Donors Can Not?
title Why Can Cationic Halogen Bond Donors Activate the Ritter-Type Solvolysis of Benzhydryl Bromide but Cationic Hydrogen Bond Donors Can Not?
title_full Why Can Cationic Halogen Bond Donors Activate the Ritter-Type Solvolysis of Benzhydryl Bromide but Cationic Hydrogen Bond Donors Can Not?
title_fullStr Why Can Cationic Halogen Bond Donors Activate the Ritter-Type Solvolysis of Benzhydryl Bromide but Cationic Hydrogen Bond Donors Can Not?
title_full_unstemmed Why Can Cationic Halogen Bond Donors Activate the Ritter-Type Solvolysis of Benzhydryl Bromide but Cationic Hydrogen Bond Donors Can Not?
title_short Why Can Cationic Halogen Bond Donors Activate the Ritter-Type Solvolysis of Benzhydryl Bromide but Cationic Hydrogen Bond Donors Can Not?
title_sort why can cationic halogen bond donors activate the ritter-type solvolysis of benzhydryl bromide but cationic hydrogen bond donors can not?
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7469379/
https://www.ncbi.nlm.nih.gov/pubmed/32905280
http://dx.doi.org/10.1021/acsomega.0c03000
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