The Effect of Benzannulation on the Structures, Reactivity and Molecular Dynamics of Indenes, Pentalenes, Azulenes and Related Molecules
The stabilising effect of benzannulation on isoindenes formed in the course of sigmatropic shifts of (C<sub>5</sub>H<sub>5</sub>)Fe(CO)<sub>2</sub> or of organo-silyl groups, and on exocyclic allyl intermediates in the course of haptotropic shifts of organometalli...
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| Format: | Article |
| Language: | English |
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MDPI AG
2022-06-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/12/3882 |
| _version_ | 1827658141849878528 |
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| author | Michael J. McGlinchey |
| author_facet | Michael J. McGlinchey |
| author_sort | Michael J. McGlinchey |
| collection | DOAJ |
| description | The stabilising effect of benzannulation on isoindenes formed in the course of sigmatropic shifts of (C<sub>5</sub>H<sub>5</sub>)Fe(CO)<sub>2</sub> or of organo-silyl groups, and on exocyclic allyl intermediates in the course of haptotropic shifts of organometallic fragments over polycyclic skeletons (fluorene, cyclopenta[<i>def</i>]phenanthrene, <i>syn</i> and <i>anti</i> dibenzpentalenes) is exemplified. This approach led to the development of the first organometallic molecular brake. Benzyne cycloadditions to anthracenes to form triptycenes also led to unexpected or multiple adducts that were characterised by X-ray crystallography. Synthetic routes to the previously elusive benz[<i>cd</i>]azulene system are presented. Finally, the complete mechanism of the stepwise assembly of dispiro- and diindenyltetracenes from fluorenylallenes is presented, whereby every intermediate has been unambiguously structurally characterised. |
| first_indexed | 2024-03-09T22:55:40Z |
| format | Article |
| id | doaj.art-f1908ce5b2c943c4a9a70110a63f393a |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T22:55:40Z |
| publishDate | 2022-06-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-f1908ce5b2c943c4a9a70110a63f393a2023-11-23T18:13:04ZengMDPI AGMolecules1420-30492022-06-012712388210.3390/molecules27123882The Effect of Benzannulation on the Structures, Reactivity and Molecular Dynamics of Indenes, Pentalenes, Azulenes and Related MoleculesMichael J. McGlinchey0School of Chemistry, University College Dublin, Belfield, D04 V1W8 Dublin 4, IrelandThe stabilising effect of benzannulation on isoindenes formed in the course of sigmatropic shifts of (C<sub>5</sub>H<sub>5</sub>)Fe(CO)<sub>2</sub> or of organo-silyl groups, and on exocyclic allyl intermediates in the course of haptotropic shifts of organometallic fragments over polycyclic skeletons (fluorene, cyclopenta[<i>def</i>]phenanthrene, <i>syn</i> and <i>anti</i> dibenzpentalenes) is exemplified. This approach led to the development of the first organometallic molecular brake. Benzyne cycloadditions to anthracenes to form triptycenes also led to unexpected or multiple adducts that were characterised by X-ray crystallography. Synthetic routes to the previously elusive benz[<i>cd</i>]azulene system are presented. Finally, the complete mechanism of the stepwise assembly of dispiro- and diindenyltetracenes from fluorenylallenes is presented, whereby every intermediate has been unambiguously structurally characterised.https://www.mdpi.com/1420-3049/27/12/3882isoindenessigmatropic and haptotropic migrationsorganometallic molecular brakedibenzpentalenesbenzyne cycloadditionsbenzazulenes |
| spellingShingle | Michael J. McGlinchey The Effect of Benzannulation on the Structures, Reactivity and Molecular Dynamics of Indenes, Pentalenes, Azulenes and Related Molecules Molecules isoindenes sigmatropic and haptotropic migrations organometallic molecular brake dibenzpentalenes benzyne cycloadditions benzazulenes |
| title | The Effect of Benzannulation on the Structures, Reactivity and Molecular Dynamics of Indenes, Pentalenes, Azulenes and Related Molecules |
| title_full | The Effect of Benzannulation on the Structures, Reactivity and Molecular Dynamics of Indenes, Pentalenes, Azulenes and Related Molecules |
| title_fullStr | The Effect of Benzannulation on the Structures, Reactivity and Molecular Dynamics of Indenes, Pentalenes, Azulenes and Related Molecules |
| title_full_unstemmed | The Effect of Benzannulation on the Structures, Reactivity and Molecular Dynamics of Indenes, Pentalenes, Azulenes and Related Molecules |
| title_short | The Effect of Benzannulation on the Structures, Reactivity and Molecular Dynamics of Indenes, Pentalenes, Azulenes and Related Molecules |
| title_sort | effect of benzannulation on the structures reactivity and molecular dynamics of indenes pentalenes azulenes and related molecules |
| topic | isoindenes sigmatropic and haptotropic migrations organometallic molecular brake dibenzpentalenes benzyne cycloadditions benzazulenes |
| url | https://www.mdpi.com/1420-3049/27/12/3882 |
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