Cp*AsCl2 (Cp* = C5Me5) reats with one equivalent of LGa (L = HC(Me)N(2,6-i-Pr2C6H3)]O-2) with formation of L(Cl)GaAs(Cl)Cp* 1, whereas the reaction with two equivalents of LGa yielded gallaarsene LGaAsCp* 2 containing a Ga=As double bond and (eta(1)-Ga(Cp*)L(eta(2)-GaL)(mu-As-3) 3. Compounds 2 and 3 were structurally characterized by single crystal X-ray diffraction, and the pi-bonding contribution in 2 was analyzed by temperature-dependent H-1 NMR spectroscopy (9.65 kcal mol(-1)) and by quantum mechanical computation.