Polyyne formation via skeletal rearrangement induced by atomic manipulation.

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^•-Br bond, triggering the rearrangement. These experiments provide structural insight into the bromo-vinyl radical intermediates, showing that the C=C^•

SUBMITTER: Pavlicek N 

PROVIDER: S-EPMC6071858 | biostudies-literature | 2018 Aug

REPOSITORIES: biostudies-literature