Diels-Alder Additions as Mechanistic Probes–Interception of Silyl-Isoindenes: Organometallic Derivatives of Polyphenylated Cycloheptatrienes and Related Seven-Membered Rings
The intermediacy of short-lived isoindenes, generated in the course of metallotropic or silatropic shifts over the indene skeleton, can be shown by Diels-Alder trapping with tetracyanoethylene, leading to the complete elucidation of the dynamic behaviour of a series of polyindenylsilanes. Cyclopenta...
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| Format: | Article |
| Language: | English |
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MDPI AG
2020-10-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/25/20/4730 |
| _version_ | 1827704305114677248 |
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| author | Michael J. McGlinchey |
| author_facet | Michael J. McGlinchey |
| author_sort | Michael J. McGlinchey |
| collection | DOAJ |
| description | The intermediacy of short-lived isoindenes, generated in the course of metallotropic or silatropic shifts over the indene skeleton, can be shown by Diels-Alder trapping with tetracyanoethylene, leading to the complete elucidation of the dynamic behaviour of a series of polyindenylsilanes. Cyclopentadienones, bearing ferrocenyl and multiple phenyl or naphthyl substituents undergo [4 + 2] cycloadditions with diaryl acetylenes or triphenylcyclopropene to form the corresponding polyarylbenzenes or cycloheptatrienes. The heptaphenyltropylium cation, [C<sub>7</sub>Ph<sub>7</sub><sup>+</sup>], was shown to adopt a nonplanar shallow boat conformation. In contrast, the attempted Diels-Alder reaction of tetracyclone and phenethynylfluorene yielded electroluminescent tetracenes. Finally, benzyne addition to 9-(2-indenyl)anthracene, and subsequent incorporation of a range of organometallic fragments, led to development of an organometallic molecular brake. |
| first_indexed | 2024-03-10T15:36:46Z |
| format | Article |
| id | doaj.art-b95c395deb6545b2b7d216504d2ce24c |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T15:36:46Z |
| publishDate | 2020-10-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-b95c395deb6545b2b7d216504d2ce24c2023-11-20T17:11:58ZengMDPI AGMolecules1420-30492020-10-012520473010.3390/molecules25204730Diels-Alder Additions as Mechanistic Probes–Interception of Silyl-Isoindenes: Organometallic Derivatives of Polyphenylated Cycloheptatrienes and Related Seven-Membered RingsMichael J. McGlinchey0School of Chemistry, University College Dublin, D04 V1W8 Belfield, Dublin 4, IrelandThe intermediacy of short-lived isoindenes, generated in the course of metallotropic or silatropic shifts over the indene skeleton, can be shown by Diels-Alder trapping with tetracyanoethylene, leading to the complete elucidation of the dynamic behaviour of a series of polyindenylsilanes. Cyclopentadienones, bearing ferrocenyl and multiple phenyl or naphthyl substituents undergo [4 + 2] cycloadditions with diaryl acetylenes or triphenylcyclopropene to form the corresponding polyarylbenzenes or cycloheptatrienes. The heptaphenyltropylium cation, [C<sub>7</sub>Ph<sub>7</sub><sup>+</sup>], was shown to adopt a nonplanar shallow boat conformation. In contrast, the attempted Diels-Alder reaction of tetracyclone and phenethynylfluorene yielded electroluminescent tetracenes. Finally, benzyne addition to 9-(2-indenyl)anthracene, and subsequent incorporation of a range of organometallic fragments, led to development of an organometallic molecular brake.https://www.mdpi.com/1420-3049/25/20/4730isoindenestetracyanoethyleneferrocenylhexaphenylcycloheptatrienetropylium ionshexanaphthylbenzeneX-ray crystallography |
| spellingShingle | Michael J. McGlinchey Diels-Alder Additions as Mechanistic Probes–Interception of Silyl-Isoindenes: Organometallic Derivatives of Polyphenylated Cycloheptatrienes and Related Seven-Membered Rings Molecules isoindenes tetracyanoethylene ferrocenylhexaphenylcycloheptatriene tropylium ions hexanaphthylbenzene X-ray crystallography |
| title | Diels-Alder Additions as Mechanistic Probes–Interception of Silyl-Isoindenes: Organometallic Derivatives of Polyphenylated Cycloheptatrienes and Related Seven-Membered Rings |
| title_full | Diels-Alder Additions as Mechanistic Probes–Interception of Silyl-Isoindenes: Organometallic Derivatives of Polyphenylated Cycloheptatrienes and Related Seven-Membered Rings |
| title_fullStr | Diels-Alder Additions as Mechanistic Probes–Interception of Silyl-Isoindenes: Organometallic Derivatives of Polyphenylated Cycloheptatrienes and Related Seven-Membered Rings |
| title_full_unstemmed | Diels-Alder Additions as Mechanistic Probes–Interception of Silyl-Isoindenes: Organometallic Derivatives of Polyphenylated Cycloheptatrienes and Related Seven-Membered Rings |
| title_short | Diels-Alder Additions as Mechanistic Probes–Interception of Silyl-Isoindenes: Organometallic Derivatives of Polyphenylated Cycloheptatrienes and Related Seven-Membered Rings |
| title_sort | diels alder additions as mechanistic probes interception of silyl isoindenes organometallic derivatives of polyphenylated cycloheptatrienes and related seven membered rings |
| topic | isoindenes tetracyanoethylene ferrocenylhexaphenylcycloheptatriene tropylium ions hexanaphthylbenzene X-ray crystallography |
| url | https://www.mdpi.com/1420-3049/25/20/4730 |
| work_keys_str_mv | AT michaeljmcglinchey dielsalderadditionsasmechanisticprobesinterceptionofsilylisoindenesorganometallicderivativesofpolyphenylatedcycloheptatrienesandrelatedsevenmemberedrings |