Theory suggests that many chemical reactions - not simply, as is often thought, redox reactions - might be catalysed by an applied electrical field. Experimental evidence for this is now provided from single-molecule studies of the formation of carbon–carbon bonds in a Diels–Alder reaction. In a series of scanning tunnelling microscopy break-junction experiments, the authors observe a fivefold increase in the frequency of single-molecule junction formation when the electrical field is present and aligned in the direction to favour electron flow from the dienophile to the diene. The demonstration that it is possible to manipulate chemical reactions with electric fields offers proof-of-principle for a novel approach to heterogeneous catalysis.
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