Synthesis and Thermal Investigations of Eleven-Membered Ring Systems Containing One of the Heavier Group 14 Element Atoms Si, Ge, and Sn
Unique eleven-membered rings containing silicon, germanium, and tin were synthesized in good yields by the reactions of the corresponding 1,2-bis((2-bromothiophen-3-yl)methoxy)benzenes with (C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>ECl<sub>2</sub> where...
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MDPI AG
2020-01-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/25/2/283 |
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| author | Nadi Eleya Clement Appiah Enno Lork Mathias Gogolin Thorsten M. Gesing Tim Stauch Anne Staubitz |
| author_facet | Nadi Eleya Clement Appiah Enno Lork Mathias Gogolin Thorsten M. Gesing Tim Stauch Anne Staubitz |
| author_sort | Nadi Eleya |
| collection | DOAJ |
| description | Unique eleven-membered rings containing silicon, germanium, and tin were synthesized in good yields by the reactions of the corresponding 1,2-bis((2-bromothiophen-3-yl)methoxy)benzenes with (C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>ECl<sub>2</sub> where E = Sn, Ge, Si. The Sn and Ge congeners were crystallized, but the conformers that these rings crystallized in, were quite different. As confirmed by Density Functional Theory (DFT) calculations, (C<sub>28</sub>H<sub>22</sub>O<sub>2</sub>S<sub>2</sub>Sn) assumes a unique crystal structure that leaves more room around the tetrel atom as compared to the crystal structure of the corresponding Ge compound. In the latter, the central cavity is quite open, whereas in the former, one of the methylene groups can fold inwards. Another consequence is the influence on the planes of the aromatic rings flanking the heterocycle. In the Ge case, the benzene ring is folded away from the central cavity, whereas in the Sn case, it is almost parallel to the imaginary axis through the center of the ring. Thermal analysis investigations (TGA and DSC methods) of these eleven-membered rings suggested the loss of a phenyl group in the first decomposition step. The decomposition temperature decreased from the Si containing heterocycle to Ge and was lowest for the Sn containing heterocycle. |
| first_indexed | 2024-12-21T08:29:50Z |
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| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-12-21T08:29:50Z |
| publishDate | 2020-01-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-80331ac2e4ce4f8d94be4aba812106422022-12-21T19:10:14ZengMDPI AGMolecules1420-30492020-01-0125228310.3390/molecules25020283molecules25020283Synthesis and Thermal Investigations of Eleven-Membered Ring Systems Containing One of the Heavier Group 14 Element Atoms Si, Ge, and SnNadi Eleya0Clement Appiah1Enno Lork2Mathias Gogolin3Thorsten M. Gesing4Tim Stauch5Anne Staubitz6Institute for Analytical and Organic Chemistry, University of Bremen, Leobener Straße 7, D-28359 Bremen, GermanyInstitute for Analytical and Organic Chemistry, University of Bremen, Leobener Straße 7, D-28359 Bremen, GermanyInstitute of Inorganic Chemistry and Crystallography, University of Bremen, Leobener Straße 7, 28359 D-Bremen, GermanyInstitute of Inorganic Chemistry and Crystallography, University of Bremen, Leobener Straße 7, 28359 D-Bremen, GermanyMAPEX Center for Materials and Processes, University of Bremen, Bibliothekstraße 1, D-28359 Bremen, GermanyMAPEX Center for Materials and Processes, University of Bremen, Bibliothekstraße 1, D-28359 Bremen, GermanyInstitute for Analytical and Organic Chemistry, University of Bremen, Leobener Straße 7, D-28359 Bremen, GermanyUnique eleven-membered rings containing silicon, germanium, and tin were synthesized in good yields by the reactions of the corresponding 1,2-bis((2-bromothiophen-3-yl)methoxy)benzenes with (C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>ECl<sub>2</sub> where E = Sn, Ge, Si. The Sn and Ge congeners were crystallized, but the conformers that these rings crystallized in, were quite different. As confirmed by Density Functional Theory (DFT) calculations, (C<sub>28</sub>H<sub>22</sub>O<sub>2</sub>S<sub>2</sub>Sn) assumes a unique crystal structure that leaves more room around the tetrel atom as compared to the crystal structure of the corresponding Ge compound. In the latter, the central cavity is quite open, whereas in the former, one of the methylene groups can fold inwards. Another consequence is the influence on the planes of the aromatic rings flanking the heterocycle. In the Ge case, the benzene ring is folded away from the central cavity, whereas in the Sn case, it is almost parallel to the imaginary axis through the center of the ring. Thermal analysis investigations (TGA and DSC methods) of these eleven-membered rings suggested the loss of a phenyl group in the first decomposition step. The decomposition temperature decreased from the Si containing heterocycle to Ge and was lowest for the Sn containing heterocycle.https://www.mdpi.com/1420-3049/25/2/283tetrelsgroup 14 elements11-membered ringsconformation |
| spellingShingle | Nadi Eleya Clement Appiah Enno Lork Mathias Gogolin Thorsten M. Gesing Tim Stauch Anne Staubitz Synthesis and Thermal Investigations of Eleven-Membered Ring Systems Containing One of the Heavier Group 14 Element Atoms Si, Ge, and Sn Molecules tetrels group 14 elements 11-membered rings conformation |
| title | Synthesis and Thermal Investigations of Eleven-Membered Ring Systems Containing One of the Heavier Group 14 Element Atoms Si, Ge, and Sn |
| title_full | Synthesis and Thermal Investigations of Eleven-Membered Ring Systems Containing One of the Heavier Group 14 Element Atoms Si, Ge, and Sn |
| title_fullStr | Synthesis and Thermal Investigations of Eleven-Membered Ring Systems Containing One of the Heavier Group 14 Element Atoms Si, Ge, and Sn |
| title_full_unstemmed | Synthesis and Thermal Investigations of Eleven-Membered Ring Systems Containing One of the Heavier Group 14 Element Atoms Si, Ge, and Sn |
| title_short | Synthesis and Thermal Investigations of Eleven-Membered Ring Systems Containing One of the Heavier Group 14 Element Atoms Si, Ge, and Sn |
| title_sort | synthesis and thermal investigations of eleven membered ring systems containing one of the heavier group 14 element atoms si ge and sn |
| topic | tetrels group 14 elements 11-membered rings conformation |
| url | https://www.mdpi.com/1420-3049/25/2/283 |
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