Theoretical Study on the Mechanism of the Thermal Retro-Cycloaddition of Isoxazolinofullerenes.
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| Title: | Theoretical Study on the Mechanism of the Thermal Retro-Cycloaddition of Isoxazolinofullerenes. |
|---|---|
| Authors: | Morera-Boado, Cercis1 cercis@fq.uh.cu, Martínez González, Marco1, Miranda-Quintana, Ramón A.1, Suárez, Margarita2, Martínez-Álvarez, Roberto1, Martín, Nazario3, García de la Vega, José M.4 |
| Source: | Journal of Physical Chemistry A. Nov2016, Vol. 120 Issue 44, p8830-8842. 13p. |
| Subjects: | Ring formation (Chemistry), Fullerene polymers, Maleic anhydride, Isoxazoline, Nitrile oxides |
| Abstract: | The retro-cycloaddition thermal reaction of isoxazolino[4,5:1,2][60]fullerenes to pristine fullerene seems to be guided by the electronic nature of the substituted nitrile oxide 1,3-dipole in the isoxazoline ring. Trapping experiments proved that the reaction mechanism occurs by thermal removal of the nitrile oxide 1,3-dipole in a process that is favored in the presence of a big excess of a highly efficient dipolarophile such as maleic anhydride. Theoretical gas phase calculations carried out at the B3LYP/6-31G(d) and M06-2X/6-31G(d) levels of theory underpin the experimental findings and predict that compound 1c, bearing the p-(CH3)2N-Ph substituent on the isoxazoline ring and with a remarkable experimental conversion efficiency in just 12 h, showed the lowest activation energy. Solvent calculations have predicted the same behavior in gas phase. Different approaches such as electrostatic natural population analysis and Houk's distortion/interaction model have been applied to understand how the electronic nature of these substituents affects the retro-cycloaddition reaction process. Analysis of the values of the condensed Fukui functions and dual descriptor shed light on the mechanism of the retro-cycloaddition reaction. [ABSTRACT FROM AUTHOR] |
| Copyright of Journal of Physical Chemistry A is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
| FullText | Text: Availability: 0 |
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| Header | DbId: egs DbLabel: Engineering Source An: 119521132 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Theoretical Study on the Mechanism of the Thermal Retro-Cycloaddition of Isoxazolinofullerenes. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Morera-Boado%2C+Cercis%22">Morera-Boado, Cercis</searchLink><relatesTo>1</relatesTo><i> cercis@fq.uh.cu</i><br /><searchLink fieldCode="AR" term="%22Martínez+González%2C+Marco%22">Martínez González, Marco</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Miranda-Quintana%2C+Ramón+A%2E%22">Miranda-Quintana, Ramón A.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Suárez%2C+Margarita%22">Suárez, Margarita</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Martínez-Álvarez%2C+Roberto%22">Martínez-Álvarez, Roberto</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Martín%2C+Nazario%22">Martín, Nazario</searchLink><relatesTo>3</relatesTo><br /><searchLink fieldCode="AR" term="%22García+de+la+Vega%2C+José+M%2E%22">García de la Vega, José M.</searchLink><relatesTo>4</relatesTo> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Journal+of+Physical+Chemistry+A%22">Journal of Physical Chemistry A</searchLink>. Nov2016, Vol. 120 Issue 44, p8830-8842. 13p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Ring+formation+%28Chemistry%29%22">Ring formation (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Fullerene+polymers%22">Fullerene polymers</searchLink><br /><searchLink fieldCode="DE" term="%22Maleic+anhydride%22">Maleic anhydride</searchLink><br /><searchLink fieldCode="DE" term="%22Isoxazoline%22">Isoxazoline</searchLink><br /><searchLink fieldCode="DE" term="%22Nitrile+oxides%22">Nitrile oxides</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: The retro-cycloaddition thermal reaction of isoxazolino[4,5:1,2][60]fullerenes to pristine fullerene seems to be guided by the electronic nature of the substituted nitrile oxide 1,3-dipole in the isoxazoline ring. Trapping experiments proved that the reaction mechanism occurs by thermal removal of the nitrile oxide 1,3-dipole in a process that is favored in the presence of a big excess of a highly efficient dipolarophile such as maleic anhydride. Theoretical gas phase calculations carried out at the B3LYP/6-31G(d) and M06-2X/6-31G(d) levels of theory underpin the experimental findings and predict that compound 1c, bearing the p-(CH3)2N-Ph substituent on the isoxazoline ring and with a remarkable experimental conversion efficiency in just 12 h, showed the lowest activation energy. Solvent calculations have predicted the same behavior in gas phase. Different approaches such as electrostatic natural population analysis and Houk's distortion/interaction model have been applied to understand how the electronic nature of these substituents affects the retro-cycloaddition reaction process. Analysis of the values of the condensed Fukui functions and dual descriptor shed light on the mechanism of the retro-cycloaddition reaction. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Journal of Physical Chemistry A is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1021/acs.jpca.6b07297 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 13 StartPage: 8830 Subjects: – SubjectFull: Ring formation (Chemistry) Type: general – SubjectFull: Fullerene polymers Type: general – SubjectFull: Maleic anhydride Type: general – SubjectFull: Isoxazoline Type: general – SubjectFull: Nitrile oxides Type: general Titles: – TitleFull: Theoretical Study on the Mechanism of the Thermal Retro-Cycloaddition of Isoxazolinofullerenes. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Morera-Boado, Cercis – PersonEntity: Name: NameFull: Martínez González, Marco – PersonEntity: Name: NameFull: Miranda-Quintana, Ramón A. – PersonEntity: Name: NameFull: Suárez, Margarita – PersonEntity: Name: NameFull: Martínez-Álvarez, Roberto – PersonEntity: Name: NameFull: Martín, Nazario – PersonEntity: Name: NameFull: García de la Vega, José M. IsPartOfRelationships: – BibEntity: Dates: – D: 10 M: 11 Text: Nov2016 Type: published Y: 2016 Identifiers: – Type: issn-print Value: 10895639 Numbering: – Type: volume Value: 120 – Type: issue Value: 44 Titles: – TitleFull: Journal of Physical Chemistry A Type: main |
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