Polyyne formation via skeletal rearrangement induced by atomic manipulation
Rearrangements that change the connectivity of a carbon skeleton are often useful in synthesis, but it can be difficult to follow their mechanisms. Scanning probe microscopy can be used to manipulate a skeletal rearrangement at the single-molecule level, while monitoring the geometry of reactants, i...
| Main Authors: | , , , , , , , |
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| Format: | Journal article |
| Language: | English |
| Published: |
Springer Nature
2018
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| _version_ | 1826278569343451136 |
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| author | Pavliček, N Gawel, P Kohn, D Majzik, Z Xiong, Y Meyer, G Anderson, H Gross, L |
| author_facet | Pavliček, N Gawel, P Kohn, D Majzik, Z Xiong, Y Meyer, G Anderson, H Gross, L |
| author_sort | Pavliček, N |
| collection | OXFORD |
| description | Rearrangements that change the connectivity of a carbon skeleton are often useful in synthesis, but it can be difficult to follow their mechanisms. Scanning probe microscopy can be used to manipulate a skeletal rearrangement at the single-molecule level, while monitoring the geometry of reactants, intermediates and final products with atomic resolution. We studied the reductive rearrangement of 1,1-dibromo alkenes to polyynes on a NaCl surface at 5 K, a reaction that resembles the Fritsch-Buttenberg-Wiechell rearrangement. Voltage pulses were used to cleave one C-Br bond, forming a radical, then to cleave the remaining C•-Br bond, triggering the rearrangement. These experiments provide structural insight into the bromo-vinyl radical intermediates, showing that the C=C•-Br unit is nonlinear. Long polyynes, up to the octayne Ph-(C≡C)8-Ph, have been prepared in this way. The control of skeletal rearrangements opens a new window on carbon-rich materials and extends the toolbox for molecular synthesis by atom manipulation. |
| first_indexed | 2024-03-06T23:45:53Z |
| format | Journal article |
| id | oxford-uuid:70dcbf56-1781-4ae1-8cda-334919c1cf37 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T23:45:53Z |
| publishDate | 2018 |
| publisher | Springer Nature |
| record_format | dspace |
| spelling | oxford-uuid:70dcbf56-1781-4ae1-8cda-334919c1cf372022-03-26T19:40:08ZPolyyne formation via skeletal rearrangement induced by atomic manipulationJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:70dcbf56-1781-4ae1-8cda-334919c1cf37EnglishSymplectic Elements at OxfordSpringer Nature2018Pavliček, NGawel, PKohn, DMajzik, ZXiong, YMeyer, GAnderson, HGross, LRearrangements that change the connectivity of a carbon skeleton are often useful in synthesis, but it can be difficult to follow their mechanisms. Scanning probe microscopy can be used to manipulate a skeletal rearrangement at the single-molecule level, while monitoring the geometry of reactants, intermediates and final products with atomic resolution. We studied the reductive rearrangement of 1,1-dibromo alkenes to polyynes on a NaCl surface at 5 K, a reaction that resembles the Fritsch-Buttenberg-Wiechell rearrangement. Voltage pulses were used to cleave one C-Br bond, forming a radical, then to cleave the remaining C•-Br bond, triggering the rearrangement. These experiments provide structural insight into the bromo-vinyl radical intermediates, showing that the C=C•-Br unit is nonlinear. Long polyynes, up to the octayne Ph-(C≡C)8-Ph, have been prepared in this way. The control of skeletal rearrangements opens a new window on carbon-rich materials and extends the toolbox for molecular synthesis by atom manipulation. |
| spellingShingle | Pavliček, N Gawel, P Kohn, D Majzik, Z Xiong, Y Meyer, G Anderson, H Gross, L Polyyne formation via skeletal rearrangement induced by atomic manipulation |
| title | Polyyne formation via skeletal rearrangement induced by atomic manipulation |
| title_full | Polyyne formation via skeletal rearrangement induced by atomic manipulation |
| title_fullStr | Polyyne formation via skeletal rearrangement induced by atomic manipulation |
| title_full_unstemmed | Polyyne formation via skeletal rearrangement induced by atomic manipulation |
| title_short | Polyyne formation via skeletal rearrangement induced by atomic manipulation |
| title_sort | polyyne formation via skeletal rearrangement induced by atomic manipulation |
| work_keys_str_mv | AT pavlicekn polyyneformationviaskeletalrearrangementinducedbyatomicmanipulation AT gawelp polyyneformationviaskeletalrearrangementinducedbyatomicmanipulation AT kohnd polyyneformationviaskeletalrearrangementinducedbyatomicmanipulation AT majzikz polyyneformationviaskeletalrearrangementinducedbyatomicmanipulation AT xiongy polyyneformationviaskeletalrearrangementinducedbyatomicmanipulation AT meyerg polyyneformationviaskeletalrearrangementinducedbyatomicmanipulation AT andersonh polyyneformationviaskeletalrearrangementinducedbyatomicmanipulation AT grossl polyyneformationviaskeletalrearrangementinducedbyatomicmanipulation |