C–F Bond Activation in the Solid State: Functionalization of Carbon through Reactions of Graphite Fluoride with Amines

Functionalization of carbon can be achieved by reactions of graphite fluoride with organic amines. Two exemplary amines, benzylamine and tetramethylethylenediamine, have been investigated. The dominant process is hydrodefluorination to form carbonaceous solids and hydrogen fluoride. Oxidative dehydrogenation of the amines provides hydrogen and concomitantly generates imines. The reactions are considered to proceed through a series of proton coupled electron transfer (PCET) steps with graphite fluoride acting as an oxidizing agent. Intermediate radicals react with the carbonaceous solids to introduce sp2 and sp3 nitrogen-containing groups into the carbon.