Scientists at the U.S. Department of Energy's (DOE) Brookhaven National Laboratory helped measure how unpaired electrons in atoms at one end of a molecule can drive chemical reactivity on the molecule's opposite side. As described in a paper recently published in the Journal of the American Chemical Society, this work, in collaboration with Princeton University, shows how molecules containing these so-called free radicals could be used in a whole new class of reactions.
"Most reactions involving free radicals take place at the site of the unpaired electron," explained Brookhaven Lab chemist Matthew Bird, one of the co-corresponding authors on the paper. The Princeton team had become experts in using free radicals for a range of synthetic applications, such as polymer upcycling. But they've wondered whether free radicals might influence reactivity on other parts of the molecule as well, by pulling electrons away from those more distant locations.
"Our measurements show that these radicals can exert powerful 'electron-withdrawing' effects that make other parts of the molecule more reactive," Bird said.
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