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Polyyne formation via skeletal rearrangement induced by atomic manipulation.
- Source :
-
Nature chemistry [Nat Chem] 2018 Aug; Vol. 10 (8), pp. 853-858. Date of Electronic Publication: 2018 Jul 02. - Publication Year :
- 2018
-
Abstract
- 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 <superscript>•</superscript> -Br bond, triggering the rearrangement. These experiments provide structural insight into the bromo-vinyl radical intermediates, showing that the C=C <superscript>•</superscript> -Br unit is nonlinear. Long polyynes, up to the octayne Ph-(C≡C) <subscript>8</subscript> -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.
Details
- Language :
- English
- ISSN :
- 1755-4349
- Volume :
- 10
- Issue :
- 8
- Database :
- MEDLINE
- Journal :
- Nature chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 29967394
- Full Text :
- https://doi.org/10.1038/s41557-018-0067-y