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Polyyne formation via skeletal rearrangement induced by atomic manipulation
Nature Chemistry ( IF 19.2 ) Pub Date : 2018-07-02 , DOI: 10.1038/s41557-018-0067-y
Niko Pavliček 1, 2 , Przemyslaw Gawel 3 , Daniel R Kohn 3 , Zsolt Majzik 1 , Yaoyao Xiong 3 , Gerhard Meyer 1 , Harry L Anderson 3 , Leo Gross 1
Affiliation  

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.



中文翻译:

通过原子操作诱导的骨架重排形成多炔

改变碳骨架连通性的重排通常在合成中很有用,但很难遵循它们的机制。扫描探针显微镜可用于在单分子水平上操纵骨架重排,同时以原子分辨率监测反应物、中间体和最终产物的几何形状。我们研究了 1,1-二溴烯烃在 5 K 的 NaCl 表面上还原重排为多炔,该反应类似于 Fritsch-Buttenberg-Wiechell 重排。电压脉冲用于裂解一个 C-Br 键,形成自由基,然后裂解剩余的 C -Br 键,触发重排。这些实验提供了对溴-乙烯基自由基中间体的结构洞察,表明 C=C –Br 单位是非线性的。以这种方式制备了长多炔,直至辛炔 Ph-(C≡C) 8 -Ph。骨架重排的控制打开了富碳材料的新窗口,并扩展了通过原子操作进行分子合成的工具箱。

更新日期:2018-07-02
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