Although alkynes have been extensively exploited in [2 + 2 + 2] cycloadditions with nitriles to form N-heterocyclic aromatics, the “alkyne-like” metal–carbon triple bond has never been used in [2 + 2 + 2] cycloadditions with nitriles. We demonstrate the synthesis of the first metallapyrazine through [2 + 2 + 2] cycloaddition reactions of a metal–carbyne complex with nitriles. Experimental observations and density functional theory calculations are evidence for the aromatic character of the metallapentalenopyrazine.