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.