Synthesis of Benzonitrile from Dinitrogen

The rhenium mediated synthesis of benzonitrile is reported with direct use of N 2 as a nitrogen source. The reaction affords benzonitrile in about 30 % overall yield upon N 2 splitting and benzylation of resulting terminal nitride. Subsequent oxidation of an intermediate phenylketimido compound restores the parent rhenium complex within a full four‐step synthetic cycle. The reaction shows that previously observed nitrile tautomerization is not a prerequisite for nitrile synthesis from N 2 with this system.