Coupling dinitrogen and hydrocarbons through aryl migration

Abstract

A persistent challenge in chemistry is to activate abundant molecules such as hydrocarbons and atmospheric N 2 , because these compounds are often inert. In particular, forming C–N bonds from N 2 typically requires a reactive organic precursor, which limits the ability to design catalytic cycles. In this article, we report an diketiminate-supported iron system that is able to sequentially activate benzene and N 2 , forming aniline derivatives. The key to this new coupling reaction is the partial silylation of a reduced iron-N 2 complex, which is followed by migratory insertion of a benzene-derived phenyl group to the nitrogen. Further reduction releases the nitrogen products, and the iron product can re-enter the resulting cyclic pathway. Using a mixture of sodium powder, crown ether, and trimethylsilyl bromide, an easily prepared diketiminate iron bromide complex can mediate the one-pot conversion of several petroleum-derived liquid compounds into the corresponding silylated aniline derivatives using N 2 as the nitrogen source. Numerous compounds along the cyclic pathway have been isolated and crystallographically characterized; their reactivity outlines the mechanism including the hydrocarbon activation step and the N 2 functionalization step. This new strategy incorporates nitrogen atoms from N 2 directly into abundant hydrocarbons.