Isolable GaN-based analogues of Thiele's and Chichibabin's hydrocarbons†

Treatment of two equivalents of Trip₂GaCl (Trip = 2,4,6-triisopropylphenyl) with pyrazine and 4,4′-bipyridine affords adducts 1 and 2 in high yields. The two-electron reduction of 1 and 2 using potassium graphite readily gives rise to the first GaN-based analogues of Thiele's and Chichibabin's hydrocarbons, Trip₂Ga(C₄N₂H₄)GaTrip₂ (3) and Trip₂Ga(C₁₀N₂H₈)GaTrip₂ (4), respectively, as crystalline solids. Structural analysis and DFT calculations suggest a closed–shell singlet ground state for both 3 and 4.